Articles and methods of making the same

ABSTRACT

The invention provides an article comprising a first layer and a second layer, and wherein the first layer is formed from a first composition comprising an ethylene/α-olefin/diene interpolymer, an isoprene rubber (synthetic), a natural rubber, a butadiene rubber, a styrene butadiene rubber, a chloroprene rubber, a nitrile rubber, a hydrogenated nitrile rubber, a chlorinated polyethylene, a chlorosulfonated polyethylene, an ethylene/propylene rubber, an ethylene/diene copolymer, a fluoro rubber, a polyurethane, a silicone rubber, or a combination thereof; and wherein the second layer is formed from a second composition comprising a butyl rubber, a halobutyl rubber, polyvinylidene chloride, a brominated polymer derived from a copolymer of isobutylene and p-methyl styrene, a nitrile rubber, a chloroprene rubber, a chlorosulfonated polyethylene, a chlorinated polyethylene, a polyurethane, a fluoro rubber, or a combination thereof.

REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.60/987,803, filed on Nov. 14, 2007, and fully incorporated herein byreference.

The invention relates to an article comprising at least two layers,where the first layer is formed from a first composition comprising anethylene/α-olefin/diene interpolymer, an isoprene rubber (synthetic), anatural rubber, a butadiene rubber, a styrene butadiene rubber, achloroprene rubber, a nitrile rubber, a hydrogenated nitrile rubber, achlorinated polyethylene, a chlorosulfonated polyethylene, anethylene/propylene rubber, an ethylene/diene copolymer, a fluoro rubber,a polyurethane, a silicone rubber, or a combination thereof; and

wherein the second layer is formed from a second composition comprisinga butyl rubber, a halobutyl rubber, a polyvinylidene chloride, abrominated polymer derived from a copolymer of isobutylene and p-methylstyrene, nitrile rubber, a chloroprene rubber, a chlorosulfonatedpolyethylene, a chlorinated polyethylene, a polyurethane, a fluororubber, or a combination thereof.

BACKGROUND

Conventional barrier structures, laminates and coextrusions contain gasbarrier materials, such as foil, polyamide, ethylene vinyl alcohol(EVOH), polyvinylidene chloride (PVDC), polyethylene terephthalate(PET), and combinations of these materials with other resins. Suchstructures can be used in various applications, such as semi permeablemembranes for the production of bladders for sportsgoods (includingbladders for footwear, sports balls, seats, inner tubes and cushioningdevices). However, these structures are relatively rigid, and do notprovide elastomeric recovery properties, in addition to excellentbarrier properties. Such structures are also frequently used inapplications such as food packaging, where the package is discardedafter opening and use. As a result, these structures and laminates arenot designed to sustain significant levels of abuse and continued re-usefor an extended period. There is a need for articles, such as films,with improved gas barrier properties, and with excellent elastomericproperties and physical abuse resistance, and which can be used for anextended periods. There is a further need for such articles for themanufacture of inner tubes and other bladder applications, which areoperated at pressures higher than atmospheric pressure. Variousapplications use semi permeable membranes for the production of bladdersfor sportsgoods (including bladders for footwear, sports balls, seats,inner tubes and cushioning devices). The article of interest contains asuper-gas which is prevented from permeating through the bladdermembrane. However, there is a need for membranes that can be used asbarriers to small molecular gases.

International Publication No. WO 2007/062669 discloses a tire comprisinga carcass structure, which comprises at least one layer formed from acrosslinked elastomeric material having air barrier properties, andwhere said crosslinked elastomeric material is obtained by crosslinkingan elastomeric composition comprising: (a) from 10 phr to 100 phr of atleast one butyl rubber; (b) from 0 phr to 90 phr of at least one dieneelastomeric polymer; (c) from 5 phr to 120 phr of at least onereinforcing filler; (d) from 2 phr to 20 phr of at least one copolymerof at least one ethylenically unsaturated carboxylic acid, or aderivative thereof, with at least one ethylenically unsaturated monomer,containing at least one polyoxyalkylene side chain (for example, seeabstract).

U.S. Pat. No. 5,992,486 discloses a laminate suitable for use with apneumatic tire having an inner liner or like air-impermeable layercapable of maintaining a requisite air pressure. One laminate includeslaminated films and a rubber layer (R); the laminated films being madeof a gas barrier layer (A) and an adhesive layer (B). The adhesive layer(B) is located on at least one side of the layer (A), and the layer (A)is formed of at least one member selected from polyamide resins,polyester resins, polyarylate resins, polyamide-based alloys andpolyester-based alloys. The laminated films are irradiated, in at leastone periphery, with an electron beam, and the adhesive layer (B) isheat-bonded to the rubber layer (R). Another laminate includes laminatedfilms and a rubber layer (R); the laminated films being made of arubber-adhering layer (D), an adhesive layer (B) and a gas barrier layer(A). The layers (D), (B) and (A) are laminated in this order, with astructure of at least three layers. The rubber-adhering layer (D) isformed of at least one polyolefin resin, the gas barrier layer (A) isformed of at least one member selected from polyamide resins, polyesterresins, polyarylate resins, polyamide-based alloys and polyester-basedalloys. The laminated films are irradiated in at least one peripherywith an electron beam, and the rubber-adhering layer (D) is heat-bondedto the rubber layer (R) (see abstract).

U.S. Pat. No. 6,579,580 discloses a composite container having a barrierproperty, and comprising packaging material. The packaging materialcomprises a base material and a co-extruded laminate layered on the basematerial. The base material has a paper support, with an inner surfaceand an outer surface, and a polyolefin resin layer, attached on theouter surface of the paper support, and constituting an outermost layerof the container. The laminate consists of a polyolefin resin layer, asecond adhesive layer, a barrier layer, a first adhesive layer, andanother polyolefin resin layer, and is arranged in this order, and hasfive layers in total. The container is formed by co-extrusion of therespective fused resins onto the base material. The former polyolefinresin layer of the laminate is directly applied onto the inner surfaceof the paper support, the latter polyolefin resin layer of the laminate,constituting an innermost layer of the container, and the barrier layercomprising polyamide resin having an aromatic moiety (see abstract).

U.S. Pat. No. 6,139,931 discloses a multi-layer closure liner forcarbonated beverage containers, and the like, which includes a gasbarrier layer, a first tie layer on an upper surface of the gas barrierlayer, a second tie layer on a lower surface of the gas barrier layer, afirst polyolefinic resin layer on the upper surface of the first tielayer, and a second polyolefinic layer on the lower surface of thesecond tie layer. In the preferred embodiment, the gas barrier layer isethylene vinyl alcohol copolymer (EVOH), the first and second tie layersare functionalized polyolefin, and the first and second polyolefinicresin layers are ethylene vinyl acetate (EVA). The layers defining theclosure liner are preferably simultaneously formed using a co-extrusionprocess to prevent the gas barrier layer from being exposed to moisture(see abstract).

Japanese Patent Disclosure No. 2003-11288 discloses a multilayeredstructural that contains a resin composition (P) layer that contains agas barrier resin (A), having the oxygen transmission rate of less than,or equal to, 500 mL·20 μm/m²·day·atm (20° C., 65%; RH), a thermoplasticresin (B) having a carbon-carbon double bond, and a transition metalsalt (C); and a resin composition (R) layer that contains a drying agent(D), and a thermoplastic resin (E). The content of the drying agent isfrom 0.1 to 50 weight percent. The thermoplastic resin (B) may be acopolymer of an aromatic vinyl compound and a diene compound. The gasbarrier resin (A) may be at least one resin selected from a polyvinylalcohol, a polyamide or a polyacrylonitrile.

U.S. Pat. No. 6,524,712 discloses a multilayer film which has at leastone first layer (1) of a thermoplastic polyurethane, at least one secondlayer (2) of a thermoplastic elastomer, and optionally a third layer (3)of a thermoplastic polyurethane. The ratio of the water vaporpermeability level of the first layer (1) to the water vaporpermeability level of the second layer (2), of the multilayer film, isat least two. When the optional third layer (3) is present in themultilayer film, the first and third layers enclose the second layer.

U.S. Pat. No. 5,941,286 discloses automotive filler tubes fabricatedfrom laminated rubbery structure of selected fluoropolymeric materialslaminated with a rubbery copolymer, like an epichlorohydrin elastomer,to provide a flexible tubular article, permitting only negligible escapeof confined volatile hydrocarbons. A FKM rubbery polymer forms arelatively thin inner layer in the tube, a THV polymer forms arelatively thin intermediate layer, and a relatively thick elastomericpolymer, e.g., ECO, forms a cover layer. In an alternative embodiment, atube is formed from an inner layer of a THV fluoroplastic polymer and acover layer of a relatively thick elastomeric polymer. The tubing ismade by coextruding the FKM rubbery polymer and the THV fluoroplasticpolymer, coating the THV fluoroplastic polymer layer with a binder,crosshead extruding the elastomeric polymer layer, and cutting thetubing to lengths. The lengths are given a partial cure in straightcondition to cross-link the THV fluoroplastic layer to the FKM rubberpolymer layer and to the elastomeric layer. The partially cured lengthsof tubing are shaped and then fully cured.

French Patent Disclosure 2650777 (Abstract) discloses a flexible tubinghaving an inner tube made of a material of the NBR nitrile, PVC-nitrileNBR-PVC or hydrogenated HNBR nitrile rubber type and fluoroelastomers.An outer tube or protective layer, coextruded with the inner tube, ismade of a material chosen from rubbers of the epichlorohydrin,chlorinated polyethylene CM, chlorosulphonated polyethylene CSM orethylene acrylate type.

U.S. Publication No. 2002/0031628 discloses a flexure endurantcomposition of an elastomer reinforced with a continuous phase ofmicroporous, expanded polytetrafluoroethylene (ePTFE) having a ratio ofelastomer to PTFE of approximately 1:1 to 50:1, on a volume basis.Examples of common synthetic elastomers include silicones, urethanes,nitrile rubber, styrene-butadiene-styrene (SBR), chloroprene,phosphazenes, fluoroelastomers, perfluoroelastomers, perfluoropolyetherelastomers, having a rubbery elastic modulus of less than 10⁷ Pa.

U.S. Publication No. 2007/0141282 discloses a multi-layer composite thathas at least one elastomer layer and at least one barrier layer. Invarious embodiments, the composite contains at least two elastomerlayers, alternating with at least two barrier layers. In otherembodiments, the composite comprises at least ten alternating barrierand elastomer layers. The barrier layer is made of an amorphous polymer,and is provided in the form of a film. Preferably, the amorphous polymerfilm has a gas transmittance rate (GTR) of less than 40cc·mil/m2·day·atm; measured as nitrogen transmittance at 0% relativehumidity at 23° C. Materials for the elastomeric layers includepolyurethane elastomers, flexible polyolefins, styrenic thermoplasticelastomers, polyamide elastomers, polyamide-ether elastomers,ester-ether or ester-ester elastomers, flexible ionomers, thermoplasticvulcanizates, flexible poly(vinyl chloride) homopolymers and copolymers,and flexible acrylic polymers.

U.S. Publication No. 2007/0065616 discloses a flexible tubular articlefor transport of volatile hydrocarbons, permitting only negligibleescape of such vapors, and comprising: (a) a relatively thin, innerlayer of an elastomeric form of an FKM fluoropolymer, and (b) one ofmore relatively thin intermediate layers of a thermoplastic form of anTHV fluoropolymer, extruded in tubular form over the inner FKM layer,and (c) a durable outer layer of an elastomeric polymer bonded to theoutside surface of the intermediate layer and being coextensivetherewith.

U.S. Pat. No. 4,776,909 discloses a coextrusion from rubber of hollowtubular structures with filament reinforcement for composites which canbe formed into spliceless bodies for pneumatic tires. The composites canbe formed from one, two, three or more rubber stocks and have portionsor layers which can form the body plies, sidewalls, innerliners,stabilizer ply inserts, and, optionally, abrasion gum strips of tirebodies. Conventional tire sidewall rubber stocks typically have a rubbercomposition comprising the following types of rubbers in the percentage(by weight) ranges: NR, 20-50%; BR, 0-60%; SBR, 30-60%; and EPDM, 0-30%.A conventional tire body rubber stock typically has a rubber compositionwithin the percentage (by weight) ranges: NR, 50-100%; BR, 30-60%; andSBR, 20-50%.

U.S. Pat. No. 5,049,220 discloses a method of preparing a pneumaticrubber tire having a decorative applique on the sidewall thereof, whichcomprises (a) applying the decorative applique to the sidewall of acured tire, and (b) binding the decorative applique to the sidewall bythe application of heat and pressure. The decorative applique comprisesfrom about 25 weight percent to about 75 weight percent syndiotactic1,2-polybutadiene, or blends of SPBD having melting points which arewithin the range of about 70° C. to about 160° C., and from about 25weight percent to about 75 weight percent of at least one polydienerubber, which is blended with the syndiotactic 1,2-polybutadiene,sulfur, zinc oxide and at least one pigment or colorant.

U.S. Pat. No. 4,967,818 discloses a method of preparing a pneumaticrubber tire having a decorative design on the sidewall thereof, whichcomprises (a) applying the decorative design to the sidewall of anuncured tire, and (b) curing the tire. The decorative design comprisesfrom about 25 weight percent to about 75 weight percent syndiotactic1,2-polybutadiene having a melting point, within the range of about 100°C. to about 160° C., and from about 25 weight percent to about 75 weightpercent of at least one polydiene rubber, which is cocurable with saidsydiotactic 1,2-polybutadiene, at least one pigment or colorant, sulfur,and zinc oxide.

U.S. Pat. No. 5,260,123 discloses block copolymers which comprisealternating blocks of (A) a polysiloxane; and (B) a copolymer of a1,3-conjugated diene and a monovinyl aromatic compound. Cured elastomercompositions exhibiting surface release characteristics are obtained bycuring a mixture comprising the above-described block copolymer in thepresence of a curing system comprising a peroxide and sulfur. Multilayerelastomer structures useful in manufacturing articles from elastomericmaterials also are described, wherein at least a portion of an outerlayer of the multilayer elastomer structure has release characteristicsand comprises the cured block copolymers of the present invention.

U.S. Pat. No. 5,957,164 discloses a barrier hose comprising an innermosttube of a thermoplastic vulcanizate. The innermost tube of thermoplasticvulcanizate is coextruded with a flexible polyamide barrier material asa second tube. A backing of thermoset rubber is extruded or calendaredover the polyamide barrier tube. A reinforcement layer follows which isthen covered with an EPDM outer cover.

U.S. Patent 2002/0179647 discloses a hydration system for providingfluid to a user. The system comprises a bladder, configured to hold afluid, which comprises an outer layer of a fluorinated rubber composite.An inner bladder layer may comprise a thermoplastic polymer, and anouter bladder, encompassing the inner bladder, may comprise afluorinated rubber. The inner bladder layer may be comprised ofthermoplastic polyurethane. The outer bladder may be comprised of amultiplayer laminate of the fluorinated rubber layer, a polyamidereinforcement layer, and a thermoplastic polymer layer.

Additional films, laminates and/or tubes are described in InternationalPublications Nos. WO2004/050358, WO2005/068191, WO2002/29299 andWO2008/091847; Japanese Patent Application Disclosure Nos. JP2004268321,JP2005335309, JP 6-328629, JP3288084A (Abstract), JP3049937A (Abstract)and JP2024137A (Abstract); Japanese Patent Application DisclosureBulletin Nos. JP 7-329252, JP 7-329261; Japanese Patent Application Nos.8-145711, and H10-109781; U.S. Publication Nos. 2004/0105945,2004/0103967 and US2005/0048236.

Butyl rubber has good barrier property for small molecular gases, and istypically used for inner tube applications. Current applications use ablend containing from 15% to 25% EPDM, and from 75% to 85% butyl rubber,to maintain acceptable barrier property and reduce cost. However, thereis a need to further reduce butyl rubber usage, or replace butyl rubberwith EPDM and/or other elastomeric polymers, to reduce cost. There is afurther need for articles that achieve much better barrier propertiesthan the incumbent articles prepared from conventional polymer blends,such as a butyl/EPDM blend. There is an additional need for articleswith improved temperature and ozone resistance relative to the incumbentbutyl/EPDM blend. These needs and others have been met by the followinginvention.

SUMMARY OF THE INVENTION

The invention provides an article comprising a first layer and a secondlayer, and wherein the first layer is formed from a first compositioncomprising an ethylene/α-olefin/diene interpolymer, an isoprene rubber(synthetic), a natural rubber, a butadiene rubber, a styrene butadienerubber, a chloroprene rubber, a nitrile rubber, a hydrogenated nitrilerubber, a chlorinated polyethylene, a chlorosulfonated polyethylene, anethylene/propylene rubber, an ethylene/diene copolymer, a fluoro rubber,a polyurethane, a silicone rubber, or a combination thereof; and

wherein the second layer is formed from a second composition comprisinga butyl rubber, a halobutyl rubber, polyvinylidene chloride, abrominated polymer derived from a copolymer of isobutylene and p-methylstyrene, nitrile rubber, a chloroprene rubber, a chlorosulfonatedpolyethylene, a chlorinated polyethylene, a polyurethane, a fluororubber, or a combination thereof.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides articles that have better barrier properties thanarticles formed from incumbent blends containing butyl rubber and anEPDM (ethylene/propylene/diene modified). The articles should alsoafford improved temperature and ozone resistance, relative to theincumbent butyl rubber/EPDM blends. The articles may contain higherlevels of EPDM, and, based on the improved oxygen barrier properties,should be producible at lower thicknesses than the incumbent articles.These features, in turn, will lower the manufacturing cost of thearticles.

Butyl rubber (or other elastomeric polymers or compounds having barrierproperty at least as good as butyl rubber) can be coextruded with EPDM,and/or other elastomeric polymers, to achieve excellent barrierproperties and good adhesion. The inventive articles are especiallysuited for inner tube applications.

In one embodiment, elastomeric polymers or compounds, with OTR (OxygenTransmission Rate) no greater than 550 cc/m²/day at ambient atmosphereare co-extruded with EPDM to form an article containing at least twolayers. These layered articles have better barrier properties thanmonolayer articles formed from incumbent butyl rubber/EPDM blends, andare especially suited for the manufacture of inner tubes. A typicalinner tube thickness is in the range of 0.8 mm to 2.6 mm.

Butyl rubber can be coextruded with EPDM to reduce the content of butylrubber, in the final structure, from 75 weight percent to 51.3 weightpercent. The resulting coextruded structure has better barrierproperties than the incumbent blend (25 weight percent EPDM plus 75weight percent butyl rubber).

As discussed above, the invention provides an article comprising a firstlayer and a second layer, and

wherein the first layer is formed from a first composition comprising anethylene/α-olefin/diene interpolymer, an isoprene rubber (synthetic), anatural rubber, a butadiene rubber, a styrene butadiene rubber, achloroprene rubber, a nitrile rubber, a hydrogenated nitrile rubber, achlorinated polyethylene, a chlorosulfonated polyethylene, anethylene/propylene rubber, an ethylene/diene copolymer, a fluoro rubber,a polyurethane, a silicone rubber, or a combination thereof; and

wherein the second layer is formed from a second composition comprisinga butyl rubber, a halobutyl rubber, a polyvinylidene chloride, abrominated polymer derived from a copolymer of isobutylene and p-methylstyrene, a nitrile rubber, a chloroprene rubber, a chlorosulfonatedpolyethylene, a chlorinated polyethylene, a polyurethane, a fluororubber, or a combination thereof.

In one embodiment, the first composition is different from the secondcomposition. For example, the first composition comprises a polymer typedifferent from that of the second composition.

In one embodiment, the article comprises at least a first layer and asecond layer.

In one embodiment, the article is formed using a melt process. In afurther embodiment, the article is formed using a process selected froma coextrusion process, a lamination process or a cast film process. In afurther embodiment, the article is formed using a process selected froma coextrusion process.

In one embodiment, the article is formed using a compression moldingprocess.

In one embodiment, the first layer and the second layer are contiguousand in direct contact.

In one embodiment, the first layer comprises a fluoro rubber. In afurther embodiment, the fluoro rubber is a crosslinkable fluoro rubber(fluoro rubber capable of forming chemical bonds between polymer chainsto form a network structure).

In one embodiment, the second layer comprises a fluoro rubber. In afurther embodiment, the fluoro rubber is a crosslinkable fluoro rubber.

In one embodiment, the first layer and the second layer, each,independently, comprises a fluoro rubber. In a further embodiment, thefluoro rubber is a crosslinkable fluoro rubber.

In one embodiment, the first layer comprises a polyurethane. In afurther embodiment, the polyurethane is a crosslinkable polyurethanerubber (polyurethane capable of forming chemical bonds between polymerchains to form a network structure).

In one embodiment, the second layer comprises a polyurethane. In afurther embodiment, the polyurethane is a crosslinkable polyurethanerubber.

In one embodiment, the first layer and the second layer, each,independently, comprises a polyurethane. In a further embodiment, thepolyurethane is a crosslinkable polyurethane rubber.

In one embodiment, the article does not contain (comprise) a reinforcingmaterial, such as a woven fabric, a nonwoven fabric and/or a metal.

In one embodiment, the article does not contain (comprise) a fiberreinforcing material.

In one embodiment, the article does not contain (comprise) a polyamide.

In one embodiment, the article does not contain (comprise) a polyester.

In one embodiment, the article does not contain (comprise) a polyvinylalcohol.

In one embodiment, the article does not contain (comprise) a blockcopolymer.

In one embodiment, the article does not contain (comprise) a polymerselected from a polyamide, a polyester, a polyvinyl alcohol, or a blockcopolymer.

In one embodiment, first composition comprises a first polymer selectedfrom the group consisting of an ethylene/α-olefin/diene interpolymer, anisoprene rubber (synthetic), a natural rubber, a butadiene rubber, astyrene butadiene rubber, a chloroprene rubber, a nitrile rubber, ahydrogenated nitrile rubber, a chlorinated polyethylene, achlorosulfonated polyethylene, an ethylene/propylene rubber, anethylene/diene copolymer, a fluoro rubber, a polyurethane rubber, and asilicone rubber; and

wherein the second composition comprises a polymer selected from thegroup consisting of a butyl rubber, a halobutyl rubber, a polyvinylidenechloride, a brominated polymer derived from a copolymer of isobutyleneand p-methyl styrene, a nitrile rubber, a chloroprene rubber, achlorosulfonated polyethylene, a chlorinated polyethylene, apolyurethane, and a fluoro rubber; and

wherein the first polymer is different from the second polymer. Forexample, the first polymer is of a polymer type different from thesecond polymer.

In one embodiment, the second layer is formed from a second compositioncomprising a butyl rubber, a halobutyl rubber, a polyvinylidenechloride, a brominated polymer derived from a copolymer of isobutyleneand p-methyl styrene, a nitrile rubber, or a combination thereof.

In one embodiment, the second layer is formed from a second compositioncomprising a butyl rubber, a halobutyl rubber, a polyvinylidenechloride, a nitrile rubber, or a combination thereof.

In one embodiment, the second layer is formed from a second compositioncomprising a butyl rubber, a polyvinylidene chloride, or a combinationthereof.

In one embodiment, the second layer is formed from a second compositioncomprising a butyl rubber.

In one embodiment, the second layer is formed from a second compositioncomprising a polyvinylidene chloride.

In one embodiment, the first layer is formed from a first compositioncomprising an ethylene/α-olefin/diene interpolymer, an isoprene rubber(synthetic), a natural rubber, a butadiene rubber, a styrene butadienerubber, an ethylene/propylene rubber, an ethylene/diene copolymer, asilicone rubber, or a combination thereof.

In one embodiment, the first layer is formed from a first compositioncomprising an ethylene/α-olefin/diene interpolymer, an isoprene rubber(synthetic), a natural rubber, a butadiene rubber, a styrene butadienerubber, an ethylene/propylene rubber, a silicone rubber, or acombination thereof.

In one embodiment, the first layer is formed from a first compositioncomprising an ethylene/α-olefin/diene interpolymer, a natural rubber, abutadiene rubber, a styrene butadiene rubber, or a combination thereof.

In one embodiment, the first layer is formed from a first compositioncomprising an ethylene/α-olefin/diene interpolymer, a styrene butadienerubber, or a combination thereof.

In one embodiment, the first layer is formed from a first compositioncomprising an ethylene/α-olefin/diene interpolymer.

In one embodiment, the second layer is adjacent to the first layer.

In one embodiment, the article comprises at least three layers.

In one embodiment, the article further comprises a third layer formedfrom a third composition comprising an ethylene/α-olefin/dieneinterpolymer. In a further embodiment, the second layer is between thefirst layer and the third layer. In yet a further embodiment, the firstlayer is formed from a composition comprising an ethylene/α-olefin/dieneinterpolymer. In a further embodiment, the second layer is formed from acomposition comprising a butyl rubber. In another embodiment, the secondlayer is formed from a composition comprising a polyvinylidene chloride.

In one embodiment, the first layer is formed from a compositioncomprising an ethylene/α-olefin/diene interpolymer, and theethylene/α-olefin/diene interpolymer is an ethylene/propylene/dieneinterpolymer. In a further embodiment, the diene is5-ethylidene-2-norbornene.

In one embodiment, the article has an Oxygen Transmission rate (OTR)less than, or equal to, 600 cc/m²/day at ambient atmosphere.

In one embodiment, the article has an Oxygen Transmission rate (OTR)less than, or equal to, 550 cc/m²/day at ambient atmosphere.

In one embodiment, the first layer has a thickness from 10 to 99percent, preferably from 15 to 75 percent, and more preferably from 25to 55 percent, based on the sum thickness of the first layer and thesecond layer.

In one embodiment, the second layer has a thickness from 1 to 90percent, preferably from 25 to 85 percent, and more preferably from 45to 75 percent, based on the sum thickness of the first layer and thesecond layer.

In one embodiment, the first layer is present in an amount from 10 to 99percent, preferably from 15 to 75 percent, and more preferably from 25to 55 percent, based on the sum thickness of the first layer and thesecond layer.

In one embodiment, the second layer is present in an amount from 1 to 90percent, preferably from 25 to 85 percent, and more preferably from 40to 75 percent, based on the sum thickness of the first layer and thesecond layer.

In one embodiment, the first layer is present in an amount from 25 to 50percent, or 25 to 45 percent, based on the sum thickness of the firstlayer and the second layer; and the second layer is present in an amountfrom 50 to 75 percent, or 55 to 75 percent, based on the sum thicknessof the first layer and the second layer.

In one embodiment, the total thickness of the article is less than, orequal to, 3500 microns, preferably less than, or equal to, 3000 microns,and more preferably less than, or equal to, 2600 microns.

In one embodiment, the total thickness of the article is greater than,or equal to, 50 microns, preferably greater than, or equal to, 100microns, and more preferably greater than, or equal to, 200 microns.

In one embodiment, the total thickness of the article is greater than,or equal to, 50 microns, preferably greater than, or equal to, 80microns.

In one embodiment, the article consists of two layers. In anotherembodiment, the article consists of three layers.

In one embodiment, the article consists of at least three layers.

In one embodiment, the article is selected from a film or a coating. Aninventive film comprises at least two layers, and is thus a multilayeredfilm.

In one embodiment, the article is a film.

In one embodiment, the article is a coating.

An inventive article may comprise a combination of two or moreembodiments as described herein.

The first composition may comprise a combination of two or moreembodiments as described herein.

The second composition may comprise a combination of two or moreembodiments as described herein.

Butyl Rubber

Butyl rubber is a copolymer of an isobutene and a conjugated diene. Inone embodiment, these copolymers contain from about 0.5 to about 5weight percent conjugated diene, based on the total weight ofpolymerizable monomers. In one embodiment, these copolymers contain fromabout 0.5 to about 5 weight percent conjugated diene, based on theweight of the copolymer. Suitable conjugated dienes include isoprene,butadiene, dimethyl butadiene, piperylene, and the like. The preferreddiene is isobutylene.

Commercial butyl rubber is a copolymer of isobutylene and minor amountsof isoprene. It is generally prepared in a slurry process using methylchloride, as a polymerization diluent, and a Friedel-Crafts catalyst,such as AlCl₃, as the polymerization initiator. The polymerization isgenerally carried out at temperatures of about −90° C. to −100° C.

Commercially available butyl rubber grades, particularly suited for usedin inner tubes applications, include butyl rubbers from ExxonMobilChemical, such as BUTYL 268; butyl rubbers from Lanxess, such as BUTYL301; butyl rubbers from Neznikamsh Russia, such as BK-1675 N; and butylrubbers from Yanchan China, such as IIR-1751.

In one embodiment, the butyl rubber has a Mooney Viscosity, ML(1+8) at125° C., greater than 30, preferably greater than 40, and morepreferably greater than 50.

In one embodiment, the butyl rubber has a Mooney Viscosity, ML(1+8) at125° C., less than 150, preferably less than 120, and more preferablyless than 100.

In one embodiment, the butyl rubber has a Mooney Viscosity ML(1+8) at125° C.) from 30 to 150, preferably from 40 to 120, and more preferablyfrom 50 to 100.

In one embodiment, the butyl rubber comprises from 1.0 to 3.0 molepercent polymerized isoprene, based on the total moles of polymerizablemonomers.

A butyl rubber may have a combination of two or more embodiments asdescribed herein.

Ethylene/α-Olefin/Diene Interpolymer

The ethylene/α-olefin/diene interpolymers (EAODMs) have polymerizedtherein ethylene, at least one α-olefin (for example, a C3-C20 α-olefinmonomer), and a diene (for example, a C4-C40 diene monomer). Theα-olefin may be either an aliphatic or an aromatic compound, and maycontain vinylic unsaturation or a cyclic compound, such as styrene,p-methyl styrene, cyclobutene, cyclopentene, and norbornene, includingnorbornene substituted in the 5 and 6 position with C1-C20 hydrocarbylgroups. Ethylenically unsaturated monomers include 4-vinylcyclohexene,vinylcyclohexane, and C3-C10 aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene). The α-olefin ispreferably a C3-C20 aliphatic compound, preferably a C3-C12 aliphaticcompound, and more preferably a C3-C8 aliphatic compound. A morepreferred C3-C10 aliphatic α-olefin is selected from the groupconsisting of propylene, 1-butene, 1-hexene and 1-octene, and morepreferably propylene. In a preferred embodiment, theethylene/α-olefin/diene interpolymer is an EPDM interpolymer. In afurther embodiment, the diene is 5-ethylidene-2-norbornene (ENB).

In one embodiment, the ethylene/α-olefin interpolymer of the presentinvention has a C2 content (polymerized ethylene) from 30 to 95 weightpercent, more preferably from 50 to 95 weight percent, and mostpreferably from 55 to 95 weight percent, or from 60 to 95 weightpercent, based on the total weight of polymerizable monomers. In oneembodiment, the ethylene/α-olefin interpolymer of the present inventionhas a C2 content (polymerized ethylene) from 30 to 95 weight percent,more preferably from 50 to 95 weight percent, and most preferably from55 to 95 weight percent, or from 60 to 95 weight percent, based on theweight of the interpolymer. In one embodiment, interpolymers alsocontain at least one α-olefin, and preferably propylene, typically at alevel of from 10 to 70 weight percent, more preferably from 10 to 50weight percent, and most preferably from 10 to 45 weight percent, or 10to 40 weight percent, based on the total weight of polymerizablemonomers. In one embodiment, interpolymers also contain at least oneα-olefin, and preferably propylene, typically at a level of from 10 to70 weight percent, more preferably from 10 to 50 weight percent, andmost preferably from 10 to 45 weight percent, or 10 to 40 weightpercent, based on the weight of the interpolymer.

In one embodiment, the interpolymer contains a non-conjugated diene, andthe non-conjugated diene content is preferably from 0.5 to 25 weightpercent, more preferably from 1 to 20 weight percent, and mostpreferably from 2 to 15 weight percent, based on total weight ofpolymerizable monomers. In one embodiment, the interpolymer contains anon-conjugated diene, and the non-conjugated diene content is preferablyfrom 0.5 to 25 weight percent, more preferably from 1 to 20 weightpercent, and most preferably from 2 to 15 weight percent, based on theweight of the interpolymer. In another embodiment, more than one dienemay be incorporated simultaneously, for example 1,4-hexadiene and ENB,with total diene incorporation within the limits specified above.

In one embodiment, the diene monomer is a non-conjugated diolefin. Thepolymerized non-conjugated diene may be used as a cure site forcross-linking. The nonconjugated diolefin can be a C6-C15 straightchain, branched chain or cyclic hydrocarbon diene. Illustrativenon-conjugated dienes are straight chain acyclic dienes, such as1,4-hexadiene and 1,5-heptadiene; branched chain acyclic dienes such as5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene,7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene,3,7-dimethyl-1,7-octadiene, 5,7-dimethyl-1,7-octadiene, 1,9-decadiene,and mixed isomers of dihydromyrcene; single ring alicyclic dienes suchas 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene;multi-ring alicyclic fused and bridged ring dienes such astetrahydroindene, methyl tetrahydroindene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes such as5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB),2-vinyl-5-norbornene (VNB), 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene and5-cyclohexylidene-2-norbornene. The diene is preferably a nonconjugateddiene selected from the group consisting of ENB, dicyclopentadiene,1,4-hexadiene, 7-methyl-1,6-octadiene, VNB, and preferably, ENB,dicyclopentadiene and 1,4-hexadiene, VNB, more preferably ENB, VNB anddicyclopentadiene, and even more preferably ENB.

In one embodiment, the diene is a conjugated diene selected from thegroup consisting of 1,3-pentadiene, 1,3-butadiene,2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene, or 1,3-cyclopentadiene.The diene monomer content, whether it comprises a conjugated diene, anon-conjugated diene or both, may fall within the limits specified abovefor non-conjugated dienes.

Although preferred ethylene/α-olefin/diene interpolymers aresubstantially free of any diene monomer that typically induces LCB, onemay include such a monomer if costs are acceptable, and desirableinterpolymer properties, such as, for example, processability, tensilestrength or elongation, do not degrade to an unacceptable level. Suchdiene monomers include dicyclopentadiene, NBD, methyl norbornadiene,vinyl-norbornene, 1,6-heptadiene, 1,7-octadiene, and 1,9-decadiene.Typically, such monomers are added in an amount within a range of fromgreater than zero to 3 weight percent, more preferably from 0.01 to 2weight percent, based on total weight of polymerizable monomers.

Preferred interpolymers of the present invention have polymerizedtherein ethylene, at least one α-olefin, and 5-ethylidene-2-norbornene(ENB). The α-olefin is preferably a C3-C20 aliphatic compound, morepreferably a C3-C12 aliphatic compound, and even more preferably a C3-C8aliphatic compound. The α-olefins include propylene, 1-butene,1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene,1-octene, 1-decene and 1-dodecene. More preferred α-olefins includepropylene, 1-butene, 1-hexene and 1-octene, and most preferablypropylene. In a preferred embodiment, the interpolymer has polymerizedtherein ethylene, propylene and 5-ethylidene-2-norbornene (ENB).

In one embodiment, the amount of ENB in the interpolymers of theinvention is from 0.5 to 15 weight percent, preferably from 1 to 10weight percent, and more preferably from 2 to 8 weight percent, based onthe total weight of polymerizable monomers.

In one embodiment, the amount of ENB in the interpolymers of theinvention is from 0.5 to 15 weight percent, preferably from 1 to 10weight percent, and more preferably from 2 to 8 weight percent, based onthe weight of the interpolymer.

In one embodiment, the α-olefin is preferably selected from the groupconsisting of C3 to C20 α-olefins, C3 to C12 α-olefins, and C3-C8α-olefins, and more preferably C3-C8 α-olefins. In a further embodiment,the α-olefin is selected from the group consisting of propylene,1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 1-heptene, and 1-octene, and preferably propylene,1-butene, 1-hexene and 1-octene. In a preferred embodiment, the α-olefinis propylene.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, employed to refer topolymers prepared from two different types of monomers, and polymersprepared from more than two different types of monomers.

The term “5-ethylidene-2-norbornene (or ENB),” as used herein, refers totwo isomeric forms of 5-ethylidene-2-norbornene((E)-5-ethylidenebicyclo[2.2.1]hept-2-ene and(Z)-5-ethylidenebicyclo[2.2.1]hept-2-ene). Commercial products of5-ethylidene-2-norbornene (or ENB) typically have a purity in the rangeof 95 weight percent to 99.9 weight percent, and where the level ofpurity is based on the amounts of the two isomeric forms of5-ethylidene-2-norbornene.

In one embodiment, the ethylene/α-olefin/diene interpolymer, EAODM (andpreferably an EPDM), is a homogeneously branched linear interpolymer ora homogeneously branched substantially linear interpolymer. In yetanother embodiment, the ethylene/α-olefin/diene interpolymer (andpreferably an EPDM) is a homogeneously branched substantially linearinterpolymer. In yet another embodiment, the ethylene/α-olefin/dieneinterpolymer (and preferably an EPDM) is a homogeneously branched linearinterpolymer.

In one embodiment, the ethylene/α-olefin/diene interpolymer is used in adry form, without an oil extender. In another embodiment, theethylene/α-olefin/diene interpolymer polymer is an EPDM interpolymer,which is used in a dry form, without an oil extender. In a furtherembodiment, the diene is 5-ethylidene-2-norbornene (ENB).

In general, polymerization may be accomplished at conditions well knownin the art for Ziegler-Natta or Kaminsky-Sinn type polymerizationreactions, that is, temperatures from 0° C. to 250° C., preferably from30° C. to 200° C., and pressures from atmospheric to 10,000 atmospheres.Polymerizations may also be conducted in accordance with processesdisclosed in U.S. Pat. No. 6,680,361 (equivalent of InternationalPublication No. WO 00/26268), fully incorporated herein by reference.Polymerizations may be performed using a suspension, solution, slurry,or gas phase polymerization, or combinations thereof. In one embodiment,the polymerization is conducted in a solution loop reactor, or isconducted in a gas phase reactor. In another embodiment, a solution fedcatalyst is used in a solution polymerization or in a gas phasepolymerization. In another embodiment, the catalyst is supported on asupport, such as, silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin), and may be spray dried ontosuch supports, and introduced in supported form into a polymerizationreactor.

The polymerization may take place in any suitable type of reactor, andpreferably a reactor design that would allow one skilled in the art todetermine catalyst efficiency. Reactors include, but are not limited to,batch reactors, continuous reactors, pilot plant reactors, a laboratoryscale reactors, a high throughput polymerization reactors, and othertypes of commercial reactors.

Inert liquids are suitable solvents for polymerization. Examples includestraight-chain and branched-chain hydrocarbons, such as isobutane,butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclicand alicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof;perfluorinated hydrocarbons, such as perfluorinated C4-C10 alkanes; andaromatic and alkyl-substituted aromatic compounds, such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins that may act as monomers or comonomers including butadiene,cyclopentene, 1-hexene, 4-vinyl-cyclohexene, vinylcyclohexane,3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene,1-decene, styrene, divinylbenzene, allylbenzene, and vinyltoluene(including all isomers alone or in admixture). Mixtures of the foregoingare also suitable. If desired, normally gaseous olefins can be convertedto liquids by application of pressure, and used herein.

Suitable catalysts for use herein, preferably include constrainedgeometry catalysts, as disclosed in U.S. Pat. Nos. 5,272,236 and5,278,272, which are both incorporated herein, in their entirety, byreference. The monocyclopentadienyl transition metal olefinpolymerization catalysts taught in U.S. Pat. No. 5,026,798, theteachings of which are incorporated herein by reference, are alsosuitable as catalysts of the invention.

The foregoing catalysts may be further described as comprising a metalcoordination complex, comprising a metal of groups 3-10 or theLanthanide series of the Periodic Table of the Elements, and adelocalized π-bonded moiety, substituted with a constrain-inducingmoiety, said complex having a constrained geometry about the metal atom,such that the angle at the metal between the centroid of thedelocalized, substituted π-bonded moiety, and the center of at least oneremaining substituent, is less than such angle in a similar complex,containing a similar π-bonded moiety lacking in such constrain-inducingsubstituent. In addition, for such complexes comprising more than onedelocalized, substituted x-bonded moiety, only one thereof, for eachmetal atom of the complex, is a cyclic, delocalized, substitutedπ-bonded moiety. The catalyst further comprises an activatingcocatalyst. Preferred catalyst complexes correspond to the Structure I:

In Structure I, M is a metal of group 3-10, or the Lanthanide series ofthe Periodic Table of the Elements;

Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound inan η5 bonding mode to M;

Z is a moiety comprising boron, or a member of group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moietyhaving up to 20 non-hydrogen atoms, and optionally Cp* and Z togetherform a fused ring system;

X independently each occurrence is an anionic ligand group or neutralLewis base ligand group having up to 30 non-hydrogen atoms;

n is 0, 1, 2, 3, or 4 and is 2 less than the valence of M; and

Y is an anionic or nonanionic ligand group bonded to Z and M comprisingnitrogen, phosphorus, oxygen or sulfur, and having up to 20 non-hydrogenatoms, optionally Y and Z together form a fused ring system. Morespecific complexes are described in U.S. Pat. Nos. 5,272,236 and5,278,272, incorporated herein by reference.

Specific compounds include: (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediylzirconium dichloride,(tert-butylamido)(tetramethyl-η5-cyclopentadienyl)1,2-ethanediyltitanium dichloride,(methylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride, (methylamido) (tetramethyl-η5cyclopentadienyl)-1,2-ethanediyltitanium dichloride,(ethylamido)(tetramethyl-η5-cyclopentadienyl)-methylenetitaniumdichloro,(tertbutylamido)dibenzyl(tetramethyl-η5-cyclopentadienyl)silanezirconiumdibenzyl,(benzylamido)dimethyl(tetramethyl-η5-cyclopentadienyl)silanetitaniumdichloride, (phenylphosphido)dimethyl(tetramethylη5-cyclopentadienyl)silanezirconium dibenzyl,(tertbutylamido)dimethyl(tetramethyl-η5-cyclopentadienyl)silanetitaniumdimethyl, and the like.

The complexes may be prepared by contacting a derivative of a metal, M,and a group I metal derivative or Grignard derivative of thecyclopentadienyl compound, in a solvent, and separating the saltbyproduct. Suitable solvents for use in preparing the metal complexesare aliphatic or aromatic liquids, such as cyclohexane,methylcyclohexane, pentane, hexane, heptane, tetrahydrofuran, diethylether, benzene, toluene, xylene, ethylbenzene, etc., or mixturesthereof.

Suitable cocatalysts for use herein include polymeric or oligomericaluminoxanes, especially methyl aluminoxane, as well as inert,compatible, noncoordinating, ion forming compounds. The so-calledmodified methyl aluminoxane (MMAO) is also suitable for use as acocatalyst. One technique for preparing such modified aluminoxane isdisclosed in U.S. Pat. No. 5,041,584, the teachings of which areincorporated herein by reference. Aluminoxanes can also be made, asdisclosed in U.S. Pat. Nos. 4,544,762; 5,015,749; and 5,041,585, theentire contents of each are incorporated herein by reference. Preferredcocatalysts are inert, noncoordinating, boron compounds, oraluminoxanes.

In addition to constrained geometry catalysts, additional single sitecatalyst systems that are suitable for use herein, include metallocenecatalyst systems and post metallocene catalyst systems.

Metallocene catalysts are, for example, coordination complexes between atransition metal, usually from group IV, in particular, titanium,zirconium or hafnium, and two, optionally substituted, cyclopentadienylligands. These catalysts are used in combination with a co-catalyst, forexample an aluminoxane, preferably methylaluminoxane, or a boroncompound (see, for example, Adv. Organomet. Chem., Vol. 18, p. 99, 10(1980); Adv. Organomet. Chem., Vol. 32, p. 325, (1991); J. M. S.-Rev.Macromol. Chem. Phys., Vol. C34(3), pp. 439-514, (1994); J.Organometallic Chemistry, Vol. 479, pp. 1-29, (1994); Angew. Chem. Int.,Ed. Engl., Vol. 34, p. 1143, (1995) Prog. Polym. Sci., Vol. 20, p. 45915 (1995); Adv. Polym. Sci., Vol. 127, p. 144, (1997); U.S. Pat. No.5,229,478, or International applications WO 93/19107, EP 129 368, EP 277003, EP 277 004, EP 632 065).

The ethylene/α-olefin/diene interpolymers of the invention may bebranched or unbranched interpolymers. The presence or absence ofbranching in the ethylene/α-olefin interpolymers, and if branching ispresent, the amount of branching, can vary widely, and may depend on thedesired processing conditions and the desired polymer properties.

The nature of the ethylene/α-olefin/diene branching can vary forconvenience. The ability to incorporate LCB (long chain branching) intopolymer backbones is known. In U.S. Pat. No. 3,821,143, a 1,4-hexadienewas used as a branching monomer to prepare ethylene/propylene/diene(EPDM) polymers having LCB. Such branching agents are sometimes referredto as H branching agents. U.S. Pat. Nos. 6,300,451 and 6,372,847 alsouse various H type branching agents to prepare polymers having LCB. InU.S. Pat. No. 5,278,272, it was discovered that constrained geometrycatalysts (CGC) have the ability to incorporate vinyl terminatedmacromonomers into the polymer backbone to form LCB polymers. Suchbranching is referred to as T type branching. Each of these patents(U.S. Pat. Nos. 3,821,143; 6,300,451; 6,372,847 and 5,278,272) is fullyincorporated herein by reference.

In one embodiment, the type of LCB in the interpolymers is T-typebranching, as opposed to H-type branching. T-type branching is typicallyobtained by copolymerization of ethylene and comonomer(s) with chain endunsaturated macromonomers, in the presence of a constrained geometrycatalyst, under the appropriate reactor conditions, such as, forexample, those described in WO 00/26268 (U.S. equivalent, U.S. Pat. No.6,680,361) or U.S. Pat. No. 5,728,272, each fully incorporated herein inby reference). If extremely high levels of LCB are desired, H-typebranching is the preferred method, since T-type branching has apractical upper limit to the degree of LCB. The T-type LCB polymers canbe produced by constrained geometry catalysts, without measurable gels,but with very high levels of T-type LCB. Because the macromonomer beingincorporated into the growing polymer chain has only one reactiveunsaturation site, the resulting polymer only contains side chains ofvarying lengths, and at different intervals along the polymer backbone.

H-type branching is typically obtained by copolymerization of ethyleneor other alpha olefins with a diene having two double bonds reactivewith a nonmetallocene type of catalyst in the polymerization process. Asthe name implies, the diene attaches one polymer molecule to anotherpolymer molecule through a diene bridge; the resulting polymer moleculeresembling an H that might be described as more of a crosslink than along chain branch. H-type branching is typically used when extremelyhigh levels of branching are desired. If too much diene is used, thepolymer molecule can form so much branching or crosslinking that thepolymer molecule is no longer soluble in the reaction solvent (in asolution process), and consequently falls out of solution, resulting inthe formation of gel particles in the polymer.

Additionally, use of H-type branching agents may deactivate metallocenecatalysts, and reduce catalyst efficiency. Thus, when H-type branchingagents are used, the catalysts used are typically not metallocenecatalysts. U.S. Pat. No. 6,372,847 discloses the use of vanadium typecatalysts to prepare H-type branched polymers.

Examples of suitable ethylene/α-olefin/diene interpolymers for use inthe invention include NORDEL hydrocarbon rubbers available from The DowChemical Company.

In one embodiment, the ethylene/α-olefin/diene interpolymer (andpreferably an EPDM) has a molecular weight distribution (Mw/Mn) lessthan 15, preferably less than 10, and more preferably less than 7. In afurther embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer (andpreferably an EPDM) has a molecular weight distribution (Mw/Mn) greaterthan 1.1, preferably greater than 1.5, and more preferably greater than2. In a further embodiment, the diene is ENB.

In one embodiment of the invention, the ethylene/α-olefin/dieneinterpolymer (EAODM) has a molecular weight distribution (Mw/Mn) from1.1 to 15, more preferably from 1.2 to 10 and most preferably from 1.5to 7. All individual values and subranges from 1.1 to 15 are includedherein and disclosed herein. In a preferred embodiment, theethylene/α-olefin/diene interpolymer is an ethylene/propylene/dieneinterpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has adensity from 0.81 to 0.96 g/cc, preferably from 0.82 to 0.95 g/cc, andmore preferably from 0.83 to 0.94 g/cc (1 cc=1 cm³). All individualvalues and subranges from 0.81 to 0.96 g/cc are included herein anddisclosed herein. In another embodiment, the ethylene/α-olefin/dieneinterpolymer has a density greater than, or equal to, 0.82 g/cc,preferably greater than, or equal to, 0.83 g/cc, and more preferablygreater than, or equal to, 0.84 g/cc. In another embodiment, theethylene/α-olefin/diene interpolymer has a density less than, or equalto, 0.96 g/cc, preferably less than, or equal to, 0.94 g/cc, and morepreferably less than, or equal to, 0.93 g/cc. In a preferred embodiment,the ethylene/α-olefin/diene interpolymer is an ethylene/propylene/dieneinterpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a Mooneyviscosity, ML(1+4) at 125° C., greater than 15, preferably greater than20, more preferably greater than 25, even more preferably greater than30, and most preferably greater than 40. In another embodiment, theethylene/α-olefin/diene interpolymer has a Mooney Viscosity, ML(1+4) at125° C., less than 200, preferably less than 140, and more preferablyless than 100. In a preferred embodiment, the ethylene/α-olefin/dieneinterpolymer polymer is an ethylene/propylene/diene interpolymer. In afurther embodiment, the diene is ENB.

In one embodiment, at ethylene/α-olefin/diene interpolymer has a Mooneyviscosity, ML(1+4) at 125° C., from 20 to 200, preferably from 25 to140, and more preferably from 30 to 100. In a preferred embodiment, theethylene/α-olefin/diene interpolymer is an ethylene/propylene/dieneinterpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a numberaverage molecular weight, (Mn) from 40,000 g/mole to 200,000 g/mole,more preferably from 50,000 g/mole to 150,000 g/mole, and mostpreferably from 60,000 g/mole to 100,000 g/mole. All individual valuesand subranges from 40,000 g/mole to 200,000 g/mole are included hereinand disclosed herein. In a preferred embodiment, theethylene/α-olefin/diene interpolymer is an ethylene/propylene/dieneinterpolymer. In a further embodiment, the diene is ENB.

In one embodiment, the ethylene/α-olefin/diene interpolymer has a weightaverage molecular weight, (Mw) from 80,000 g/mole to 500,000 g/mole,more preferably from 100,000 g/mole to 400,000 g/mole, and mostpreferably from 120,000 g/mole to 370,000 g/mole. All individual valuesand subranges from 80,000 g/mole to 500,000 g/mole are included hereinand disclosed herein. In a preferred embodiment, theethylene/α-olefin/diene interpolymer is an ethylene/propylene/dieneinterpolymer. In a further embodiment, the diene is ENB.

An ethylene/α-olefin/diene interpolymer may comprise a combination oftwo or more embodiments as described herein.

Isoprene Rubber

Isoprene rubbers (polyisoprenes) include both natural polyisoprene andsynthetic polyisoprene. Suitable polyisoprenes include, but are notlimited to, natural cis-1,4-polyisoprene (example, natural rubber),synthetic cis-1,4-polyisoprene, high vinyl 3,4-polyisoprene and3,4-polyisoprene.

In one embodiment, the isoprene rubber has a Mooney Viscosity (ML 1+4 at100° C.) greater than, or equal to, 20, preferably greater than, orequal to, 30, and more preferably greater than, or equal to 40.

In one embodiment, the isoprene rubber has a Mooney Viscosity (ML 1+4 at100° C.) less than, or equal to, 100, preferably less than, or equal to,80, and more preferably less than, or equal to 70.

In one embodiment, the isoprene rubber has a Mooney Viscosity (ML 1+4 at100° C.) from 20 to 100, and preferably from 30 to 80, and morepreferably from 40 to 70.

Suitable examples of isoprene rubbers include the following technicalgrades: SMR (Standard Malaysian Rubber), such as SMR 5 and SMR 20; TSR(Technical Specified Rubber) and RSS (Ribbed Smoked Sheets).

In one embodiment, the isoprene rubber is a naturalcis-1,4-polyisoprene. In another embodiment, the isoprene rubber is asynthetic cis-1,4-polyisprene.

An isoprene rubber may have a combination of two or more embodiments asdescribed herein.

Butadiene Rubber

Suitable butadiene rubbers (polybutadienes) include, but are not limitedto, natural cis-1,4-polybutadiene, trans-1,4-polybutadiene,vinyl-1,2-polybutadiene, copolymers of styrene and butadiene, copolymersof isoprene and butadiene, and interpolymers of styrene, isoprene andbutadiene.

In one embodiment, the butadiene rubber has a Mooney Viscosity (ML 1+4at 100° C.) greater than, or equal to, 10, preferably greater than, orequal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the butadiene rubber has a Mooney Viscosity (ML 1+4at 100° C.) less than, or equal to, 100, preferably less than, or equalto, 90, and more preferably less than, or equal to 80.

In one embodiment, the butadiene rubber has a Mooney Viscosity (ML 1+4at 100° C.) from 10 to 100, preferably from 15 to 90, and morepreferably from 20 to 80.

Examples of suitable butadiene rubbers include EUROPRENE NEOCIS BRrubbers, such as EUROPRENE NEOCIS BR 40 from Polimeri Europa; BUNA CBrubbers, such as BUNA CB 24 from Lanxess; and SE BR synthetic rubbers,such as SE BR-1220M from The Dow Chemical Company.

A butadiene rubber may have a combination of two or more embodiments asdescribed herein.

Styrene Butadiene Rubber (SBR)

Suitable styrene butadiene rubbers include, but are not limited to, coldpolymerized emulsion SBR and solution polymerized SBR.

In one embodiment, the styrene butadiene rubber has a Mooney Viscosity(ML 1+4 at 100° C.) greater than, or equal to, 10, preferably greaterthan, or equal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the styrene butadiene rubber has a Mooney Viscosity(ML 1+4 at 100° C.) less than, or equal to, 200, preferably less than,or equal to, 150, and more preferably less than, or equal to 100.

In one embodiment, the styrene butadiene rubber has a Mooney Viscosity(ML1+4 at 100° C.) from 10 to 200, preferably from 15 to 150, and morepreferably from 20 to 100.

In one embodiment, the styrene butadiene rubber has a bound styrenecontent (ASTM D5775) from 5 to 80 percent, preferably from 10 to 70percent, and more preferably from 15 to 60 percent, based on the totalweight of polymerizable monomers.

In one embodiment, the styrene butadiene rubber has a bound styrenecontent (ASTM D5775) from 5 to 80 percent, preferably from 10 to 70percent, and more preferably from 15 to 60 percent, based on the weightof the styrene butadiene rubber.

Examples of suitable styrene butadiene rubbers include BUNA SB rubbers,such as BUNA SB 1500-Schkopau; and SE SLR synthetic rubbers, such as SESLR-4400 from The Dow Chemical Company.

A styrene butadiene rubber may have a combination of two or moreembodiments as described herein.

Chloroprene Rubber

Suitable chloroprene rubbers (polychloroprenes) include, but are notlimited to, homopolymers of chloroprene, sulfur-modified copolymers, andcopolymers of chloroprene and 2,3-dichloro-1,3-butadiene.

In one embodiment, the chloroprene rubber has a Mooney Viscosity (ML 1+4at 100° C.) greater than, or equal to, 10, preferably greater than, orequal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the chloroprene rubber has a Mooney Viscosity (ML 1+4at 100° C.) less than, or equal to, 200, preferably less than, or equalto, 150, and more preferably less than, or equal to 125.

In one embodiment, the chloroprene rubber has a Mooney Viscosity (ML1+4at 100° C.) from 10 to 200, preferably from 15 to 150, and morepreferably from 20 to 125.

In another embodiment, the chloroprene rubber has a specific gravity(ASTM D792) from 1.20 to 1.25 g/cc.

Examples of suitable chloroprene rubbers include NEOPRENEpolychloroprenes, such as NEOPRENE WRT from DuPont PerformanceElastomers, and SKYPRENE chloroprene rubbers, such as SKYPRENE E-20 fromTOSOH. (Neoprene is the Product Name and Wrt is the Grade)

A chloroprene rubber may have a combination of two or more embodimentsas described herein.

Nitrile Rubber (NBR)

Suitable nitrile rubbers include, but are not limited to, copolymers ofacrylonitrile and butadiene, hot or cold polymerized.

In one embodiment, the nitrile rubber has a Mooney Viscosity (ML 1+4 at100° C.) greater than, or equal to, 15, preferably greater than, orequal to, 20, and more preferably greater than, or equal to 25.

In one embodiment, the nitrile rubber has a Mooney Viscosity (ML 1+4 at100° C.) less than, or equal to, 150, preferably less than, or equal to,140, and more preferably less than, or equal to 130.

In one embodiment, the nitrile rubber has a Mooney Viscosity (ML1+4 at100° C.) from 15 to 150, preferably from 20 to 140, and more preferablyfrom 25 to 130.

In one embodiment, the nitrile rubber has a bound acrylonitrile content(ASTM D 3533) from 20 to 80 weight percent, preferably from 25 to 70weight percent, more preferably from 30 to 60 weight percent, based ontotal weight of polymerizable monomers.

In one embodiment, the nitrile rubber has a bound acrylonitrile contentfrom 20 to 80 weight percent, preferably from 25 to 70 weight percent,more preferably from 30 to 60 weight percent, based on the weight of thenitrile rubber.

Examples of suitable nitrile rubbers include NITRIFLEX nitrile rubbers,such as Nitrile Rubber N-206 from NITRIFLEX.

A nitrile rubber may have a combination of two or more embodiments asdescribed herein.

Hydrogenated Nitrile Rubber (HNBR)

In one embodiment, the hydrogenated nitrile rubber has a MooneyViscosity (ML 1+4 at 100° C.) greater than, or equal to, 20, preferablygreater than, or equal to, 30, and more preferably greater than, orequal to 40.

In one embodiment, the hydrogenated nitrile rubber has a MooneyViscosity (ML 1+4 at 100° C.) less than, or equal to, 120, preferablyless than, or equal to, 110, and more preferably less than, or equal to100.

In one embodiment, the hydrogenated nitrile rubber has a MooneyViscosity (ML1+4 at 100° C.) from 20 to 120, preferably from 30 to 110,and more preferably from 40 to 100.

Examples of suitable hydrogenated nitrile rubbers include THERBANhydrogenated nitrile rubbers, such as THERBAN C4367 from Lanxess.

A hydrogenated nitrile rubber may have a combination of two or moreembodiments as described herein.

Chlorinated Polyethylene

In one embodiment, the chlorinated polyethylene has a Mooney Viscosity(ML 1+4 at 121° C.) greater than, or equal to, 30, preferably greaterthan, or equal to, 40, and more preferably greater than, or equal to 50.

In one embodiment, the chlorinated polyethylene has a Mooney Viscosity(ML 1+4 at 121° C.) less than, or equal to, 130, preferably less than,or equal to, 120, and more preferably less than, or equal to 110.

In one embodiment, chlorinated polyethylene has a Mooney Viscosity(ML1+4 at 121° C.) from 30 to 130, preferably from 40 to 120, and morepreferably from 50 to 110.

In another embodiment, chlorinated polyethylene has a specific gravity(ASTM D792) from 1.10 to 1.20 g/cc.

Examples of suitable chlorinated polyethylene include TYRIN chlorinatedpolyethylenes, such as TYRIN CM0136 from The Dow Chemical Company.

A chlorinated polyethylene may have a combination of two or moreembodiments as described herein.

Chlorosulfonated Polyethylene

In one embodiment, the chlorosulfonated polyethylene has a MooneyViscosity (ML 1+4 at 100° C.) greater than, or equal to, 10, preferablygreater than, or equal to, 15, and more preferably greater than, orequal to 20.

In one embodiment, the chlorosulfonated polyethylene has a MooneyViscosity (ML 1+4 at 100° C.) less than, or equal to, 140, preferablyless than, or equal to, 130, and more preferably less than, or equal to120.

In one embodiment, chlorosulfonated polyethylene has a Mooney Viscosity(ML1+4 at 100° C.) from 10 to 140, preferably from 15 to 130, and morepreferably from 20 to 120.

In another embodiment, chlorosulfonated polyethylene has a specificgravity from 1.05 to 1.30 g/cc

Examples of suitable chlorosulfonated polyethylenes include HYPALONchlorosulfonated polyethylenes, such as HYPALON 30 from DupontPerformance Elastomers; and TOSO CSM chlorosulfonated polyethylenes,such as TOSO-CSM TS-430 from TOSOH.

A chlorosulfonated polyethylene may have a combination of two or moreembodiments as described herein.

Ethylene/Propylene Rubber

In one embodiment, the ethylene/propylene rubber has a Mooney Viscosity(ML 1+4 at 125° C.) greater than, or equal to, 10, preferably greaterthan, or equal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the ethylene/propylene rubber has a Mooney Viscosity(ML 1+4 at 125° C.) less than, or equal to, 200, preferably less than,or equal to, 150, and more preferably less than, or equal to 100.

In one embodiment, ethylene/propylene rubber has a Mooney Viscosity(ML1+4 at 125° C.) from 10 to 200, preferably from 15 to 150, and morepreferably from 20 to 100.

Examples of suitable ethylene/propylene rubbers include VIS TALONrubbers, such as VISTALON EPM 404 from ExxonMobil Chemical; and JSR EPrubbers, such as JSR EP 11 from JSR Corporation.

An ethylene/propylene rubber may have a combination of two or moreembodiments as described herein.

Ethylene/α-Olefin Interpolymer

Suitable ethylene/α-olefin interpolymers include, but not limited to,copolymers of ethylene and butene, and copolymers of ethylene andoctene.

In one embodiment, the ethylene/α-olefin interpolymer, and preferably anethylene/α-olefin copolymer, has a density greater than, or equal to,0.84 g/cc, preferably greater than, or equal to, 0.85 g/cc, and morepreferably greater than, or equal to, 0.86 g/cc.

In one embodiment, the ethylene/α-olefin interpolymer, and preferably anethylene/α-olefin copolymer, has a density less than, or equal to, 0.95g/cc, preferably less than, or equal to, 0.93 g/cc, and more preferablyless than, or equal to, 0.91 g/cc.

In one embodiment, ethylene/α-olefin interpolymer, and preferably anethylene/α-olefin copolymer, has a density (ASTM D792) from 0.84 to0.95, preferably from 0.85 to 0.93, and more preferably from 0.86 to0.91.

In one embodiment, ethylene/α-olefin interpolymer, and preferably anethylene/α-olefin copolymer, has a Mooney Viscosity (ML 1+4 at 121° C.)greater than, or equal to, 2, preferably greater than, or equal to, 5,and more preferably greater than, or equal to, 7.

In one embodiment, the ethylene/α-olefin interpolymer, and preferably anethylene/α-olefin copolymer, has a Mooney Viscosity (ML 1+4 at 125° C.)less than, or equal to, 90, preferably less than, or equal to, 80, andmore preferably less than, or equal to, 70.

Examples of suitable ethylene/α-olefin copolymers include ENGAGEpolyolefin elastomers, such as ENGAGE 7387 and ENGAGE 8180, availablefrom The Dow Chemical Company; and EXACT polymers available fromExxonMobil Chemical.

An ethylene/α-olefin interpolymer, and preferably an ethylene/α-olefincopolymer, may have a combination of two or more embodiments asdescribed herein.

Ethylene/Diene Copolymer

Suitable ethylene/diene copolymers include copolymers of ethylene andnonconjugated or conjugated dienes.

In one embodiment, ethylene/diene copolymer has a Mooney Viscosity (ML1+4 at 121° C.) greater than, or equal to, 2, preferably greater than,or equal to, 5, and more preferably greater than, or equal to, 7.

In one embodiment, the ethylene/diene copolymer has a Mooney Viscosity(ML 1+4 at 125° C.) less than, or equal to, 90, preferably less than, orequal to, 80, and more preferably less than, or equal to, 70.

In another embodiment, ethylene/diene copolymer has a Mooney Viscosity(ML1+4 at 121° C.) from 2 to 90, preferably from 5 to 80, and morepreferably from 7 to, 70.

In one embodiment, the diene monomer is a non-conjugated diolefin. Thenonconjugated diolefin can be a C6-C15 straight chain, branched chain orcyclic hydrocarbon diene. Illustrative nonconjugated dienes are straightchain acyclic dienes, such as 1,4-hexadiene and 1,5-heptadiene; branchedchain acyclic dienes such as 5-methyl-1,4-hexadiene,2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene,3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene,5,7-dimethyl-1,7-octadiene, 1,9-decadiene, and mixed isomers ofdihydromyrcene; single ring alicyclic dienes such as 1,4-cyclohexadiene,1,5-cyclooctadiene and 1,5-cyclododecadiene; multi-ring alicyclic fusedand bridged ring dienes such as tetrahydroindene, methyltetrahydroindene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidenenorbornenes such as 5-methylene-2-norbornene (MNB),5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene,5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene and 5-cyclohexylidene-2-norbornene. Thediene is preferably a nonconjugated diene selected from the groupconsisting of ENB, dicyclopentadiene, 1,4-hexadiene,7-methyl-1,6-octadiene, and preferably, ENB, dicyclopentadiene and1,4-hexadiene, more preferably ENB and dicyclopentadiene, and even morepreferably ENB.

In another embodiment, the diene is a conjugated diene. The conjugateddiene may be selected from the group consisting of 1,3-pentadiene,1,3-butadiene, 2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene, or1,3-cyclopentadiene.

An ethylene/diene copolymer may have a combination of two or moreembodiments as described herein.

Fluoro Rubber

Suitable fluoro rubbers include, but are not limited to, copolymers ofperfluoro methylvinyl ether, vinylidene fluoride, andtetra-fluoroethylene, copolymers of ethylene, tetrafluoroethylene andperfluoromethylvinyl ether, copolymers of hexafluoro-propylene,vinylidene fluoride, and tetra-fluoroethylene, and copolymers ofhexafluoropropylene and vinylidene fluoride.

In one embodiment, the fluoro rubber has a Mooney Viscosity (ML 1+4 at121° C.) greater than, or equal to, 10, preferably greater than, orequal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the fluoro rubber has a Mooney Viscosity (ML 1+4 at121° C.) less than, or equal to, 170, preferably less than, or equal to,160, and more preferably less than, or equal to 100.

In one embodiment, the fluoro rubber has a Mooney Viscosity (ML1+10 at121° C.) from 10 to 170, preferably from 15 to 160, and more preferablyfrom 20 to 100.

In another embodiment, the fluoro rubber has a specific gravity from1.70 to 1.90 g/cc.

Examples of fluoro rubbers include VITON elastomers, such as VITON A-500fluoroelastomer from DuPont Performance Elastomers.

A fluoro rubber may comprise a combination of two or more embodiments asdescribed herein.

Polyurethane

In one embodiment, the polyurethane has a Mooney Viscosity (ML 5+4 at100° C.) greater than, or equal to, 10, preferably greater than, orequal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the polyurethane has a Mooney Viscosity (ML 5+4 at100° C.) less than, or equal to, 100, preferably less than, or equal to,75, and more preferably less than, or equal to 60.

In one embodiment, polyurethane has a Mooney Viscosity (ML 5+4 at 100°C.) from 10 to 100, preferably from 15 to 75, and more preferably from20 to 60.

Examples of suitable polyurethane rubber include UREPAN polyurethanes,such as UREPAN 640 G from Rhein Chemie.

In one embodiment, the polyurethane is a thermoplastic polyurethane.

In a preferred embodiment, the polyurethane is a crosslinkablepolyurethane.

The polyurethane may comprise a combination of two or more embodimentsas described herein.

Silicone Rubber

In one embodiment, the silicon rubber has a density greater than, orequal to, 1.02 g/cc, preferably greater than, or equal to, 1.04 g/cc,and more preferably greater than, or equal to, 1.06 g/cc.

In one embodiment, the silicon rubber as a density less than, or equalto, 1.25 g/cc, preferably less than, or equal to, 1.23 g/cc, and morepreferably less than, or equal to, 1.22 g/cc.

In one embodiment, the silicone rubber has a density from 1.02 to 1.25g/cc, preferably from 1.04 to 1.23 g/cc, and more preferably from 1.06to 1.22 g/cc.

Examples of suitable silicone rubbers include SILASTIC siliconeelastomers, such as SILASTIC Q7-4535 from Dow Corning.

Halobutyl Rubber

Suitable halobutyl rubbers include, but are not limited to, chlorobutyland bromobutyl rubbers.

In one embodiment, the halobutyl rubber has a Mooney Viscosity (ML1+8 at125° C.) greater than, or equal to, 20, preferably greater than, orequal to, 23, and more preferably greater than, or equal to, 25.

In one embodiment, the halobutyl rubber has a Mooney Viscosity (ML1+8 at125° C.) less than, or equal to, 90, preferably less than, or equal to,80, and more preferably less than, or equal to, 70.

In one embodiment, halobutyl rubber has a Mooney Viscosity (ML1+8 at125° C.) from 20 to 90, preferably from 23 to 80, and more preferablyfrom 25 to 70.

Examples of suitable halobutyl rubbers include EXXON bromobutyl rubbers,such as EXXON BROMOBUTYL 2255, and EXXON chlorobutyl rubbers, such asEXXON CHLOROBUTYL 1068, available from ExxonMobil Chemical.

Polyvinylidene Chloride

In one embodiment, polyvinylidene chloride has a DSC melting temperaturefrom 130° C. to 190° C., preferably from 135° C. to 180° C., and morepreferably from 140° C. to 175° C.

Examples of suitable polyvinylidene chlorides include SARAN resins, suchas SARAN Resin 168 from The Dow Chemical Company.

Brominated Polymers Derived from a Copolymer of Isobutylene and p-MethylStyrene

In one embodiment, the brominated polymer has a Mooney Viscosity (ML1+8at 125° C.) greater than, or equal to, 10, preferably greater than, orequal to, 15, and more preferably greater than, or equal to 20.

In one embodiment, the brominated polymer has a Mooney Viscosity (ML1+8at 125° C.) less than, or equal to, 80, preferably less than, or equalto, 70, and more preferably less than, or equal to 60.

In one embodiment, the brominated polymer has a Mooney Viscosity (ML1+8at 125° C.) from 10 to 80, preferably from 15 to 70, and more preferablyfrom 20 to 60.

Examples of suitable brominated polymers include EXXPRO elastomers, suchas EXXPRO 3433 available from ExxonMobil Chemical.

Compositions

The compositions used to form the first layer and the second layer of aninventive article may each, independently, contain one or moreadditives, including, but not limited to, antioxidants, UV stabilizers,anti-ozonants, fillers, plasticizers, vulcanization accelerators,crosslinking agents, flame retardants, and processing aids.

Additional additives include, but are not limited to, lubricants;processing oils, antioxidants such as phenolics, secondary amines,phosphites and thioesters; fillers and reinforcing agents such as carbonblack, glass, metal carbonates such as calcium carbonate, metal sulfatessuch as calcium sulfate, talc, clay or graphite fibers; hydrolyticstabilizers; lubricants such as fatty acids, fatty alcohols, esters,fatty amides, metallic stearates, paraffinic and microcrystalline waxes,silicones and orthophosphoric acid esters; acid neutralizers or halogenscavengers such as zinc oxide; mold release agents such as fine-particleor powdered solids, soaps, waxes, silicones, polyglycols and complexesters such as trimethylol propane tristearate or pentaerythritoltetrastearate; pigments, dyes and colorants; heat stabilizers such asorganotin mercaptides, an octyl ester of thioglycolic acid and a bariumor cadmium carboxylate; ultraviolet light stabilizers such as a hinderedamine, an o-hydroxy-phenylbenzotriazole, a2-hydroxy-4-alkoxybenzophenone, a salicylate, a cyanoacrylate, a nickelchelate and a benzylidene malonate and oxalanilide; acid-scavengers; andzeolites, molecular sieves and other known deodorizers. Other additivesinclude scratch/mar additives, such as polydimethyl siloxane (PDMS) orfunctionalized polydimethyl siloxane or IRGASURF SR 100 (available fromCiba Specialty Chemicals) or scratch mar formulations containingerucamide.

Stabilizer and antioxidants may be added to a resin formulation toprotect the resin from degradation, caused by reactions with oxygen,which are induced by such things as heat, light or residual catalystfrom the raw materials. Antioxidants are commercially available fromCiba-Geigy, located in Hawthorn, N.Y., and include IRGANOX 565, 1010 and1076, which are hindered phenolic antioxidants. These are primaryantioxidants, which act as free radical scavengers, and may be usedalone or in combination with other antioxidants, such as phosphiteantioxidants, like IRGAFOS 168, available from Ciba-Geigy. Phosphiteantioxidants are considered secondary antioxidants, are not generallyused alone, and are primarily used as peroxide decomposers. Otheravailable antioxidants include, but are not limited to, CYANOX LTDP,available from Cytec Industries in Stamford, Conn., and ETHANOX 1330,available from Albemarle Corp. in Baton Rouge, La. Many otherantioxidants are available for use by themselves, or in combination withother such antioxidants.

Antioxidants and antiozonants additives include hindered phenols,bisphenols, and thiobisphenols; substituted hydroquinones;tris(alkylphenyl)phosphites; dialkylthiodipropionates;phenylnaphthylamines; substituted diphenylamines; dialkyl, alkyl aryl,and diaryl substituted p-phenylene diamines; monomeric and polymericdihydroquinolines;2-(4-hydroxy-3,5-t-butylaniline)-4,6-bis(octylthio)1,3,5-triazine,hexahydro-1,3,5-tris-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine,2,4,6-tris(n-1,4-dimethylpentylpphenylenediamino)-1,3,5-triazine,tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, nickeldibutyldithiocarbamate, 2-mercaptotolylimidazole and its zinc salt,petroleum waxes, and the like.

In one embodiment, a composition further comprises the at least onefiller selected from the group consisting of silica; carbon black; clay;titanium dioxide; silicates of aluminum, magnesium, calcium, sodium,potassium and mixtures thereof; carbonates of calcium, magnesium andmixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, andaluminum; sulfates of calcium, barium, and lead; alumina trihydrate;magnesium hydroxide and mixtures thereof. In one embodiment, compositionfurther comprises at least one filler. In a further embodiment, the atleast one filler is carbon black.

In one embodiment, a composition, independently, further comprises atleast one additive selected from the group consisting of pigment,antioxidants, flame retardants, scratch and mar resistant additives, andcombinations thereof.

Other additives include, but are not limited to, one or more oils andone or more plasticizers. Plasticizers include, but are not limited to,petroleum oils such as ASTM D2226 aromatic oils; paraffinic andnaphthenic oils; polyalkylbenzene oils; organic acid monoesters such asalkyl and alkoxyalkyl oleates and stearates; organic acid diesters suchas dialkyl, dialkoxyalkyl, and alkyl aryl phthalates, terephthalates,sebacates, adipates, and glutarates; glycol diesters such as tri-,tetra-, and polyethylene glycol dialkanoates; trialkyl trimellitates;trialkyl, trialkoxyalkyl, alkyl diaryl, and triaryl phosphates;chlorinated paraffin oils; coumarone-indene resins; pine tars; vegetableoils such as castor, tall, rapeseed, and soybean oils and esters andepoxidized derivatives thereof; esters of dibasic acids (or theiranhydrides) with monohydric alcohols such as o-phthalates, adipates andbenzoates; and the like. Additional examples of suitable oils includethose listed as ester plasticizers in Ellul, U.S. Pat. No. 6,326,426,which is incorporated herein. An artisan skilled in the processing ofelastomers and rubber compositions will recognize which type of oil willbe most beneficial. In one embodiment, a composition further comprisesat least one oil or at least one plasticizer. In a further embodiment,the at least one oil or the at least one plasticizer is present in anamount less than 30 weight percent, based on the total weight of thecomposition.

In one embodiment, a composition contains flame retardant, such as ametal hydrate, such as aluminum trihydroxide, magnesium dihydroxide, orcombinations thereof. A further description of such flame retardants isfound in International Publication No. WO 2005/023924, fullyincorporated herein by reference.

In one embodiment, a composition contains a flame retardant package thatincludes a halogenated alkane flame retardant, an aromatic halogenatedflame retardant, and optionally a flame retardant synergist. In yetanother embodiment, the flame retardant synergist comprises one or moreof a metal oxide, halogenated paraffin, triphenylphosphate,dimethyldiphenylbutane, polycumyl, or a combination thereof. A furtherdescription of such flame retardants is found in InternationalPublication No. WO 2002/12377, fully incorporated herein by reference.

A composition may also comprise an ethylene homopolymer or ethyleneinterpolymer grafted with maleic anhydride or succinic anhydride groups,and preferably the grafted ethylene homopolymer or interpolymercomprises less than 20 percent of said composition. In yet a furtherembodiment, the composition also includes at least one additive, such asa plasticizer, a pigment or colorant, a UV stabilizer, or a filler.Fillers may include calcined or uncalcined fillers. Suitable fillersinclude, but are not limited to calcium carbonate and wollastonite.Suitable components for scratch mar resistant formulations are describedin more detail in U.S. Pat. No. 5,902,854, fully incorporated herein byreference.

In one embodiment, a composition comprises one or more crosslinkingagents.

In one embodiment, at least one composition, independently, furthercomprises at least one crosslinking agent, one crosslinking activator incombination with a fatty acid and one crosslinking accelerator.

In one embodiment, the crosslinking agent is selected from the groupconsisting of sulfur-containing compounds, peroxides, and phenoliccompounds.

Crosslinking agents include, but are not limited to, crosslinkingmaterials or curatives which do not require the addition of a curing orcrosslinking activator and accelerators. Crosslinking agents alsoinclude crosslinking materials or curatives which require the additionof a cure activator or crosslinking activator, mainly metal oxides,which include zinc oxide, hydrated lime, litharge, red lead, white lead,magnesium oxide, alkali carbonates, and hydroxides Zinc oxide is themost common, and it is generally used in combination with a fatty acid,such as stearic acid, to form a rubber soluble soap in the rubbermatrix. Crosslinking agents also include crosslinking materials orcuratives, which require the addition of a cure or one or morecrosslinking accelerators. Examples of suitable cure or crosslinkingaccelerators include aniline, diphenylguanidine, hexmethylene tetramine,mercaptobenzothiazole and its zinc salt, benzothiazyl disulfide,4,4′-dithiodimorpholine, zinc-0,0-dibutylphosphorodithioate,sulfenamides, thiurams, dithiocarbamates and xanthates. If acrosslinking agent is used, which requires the further addition of acrosslinking or cure activator, either the cure activator or thecrosslinking agent, or both, can be encapsulated. Typically, when anencapsulated cure system is used, a crosslinking agent which requiresthe addition of a cure activator or crosslinking activator is used.

Any suitable crosslinking agent, or combination of crosslinking agents,may be used in the practice of this invention. Examples of suitablecrosslinking agents are accelerated sulfur systems, including efficientand semi-efficient systems; peroxide systems, alone or with co-agents;phenolic resin curative systems; phenylenebismaleimide; urethanecuratives; grafted alkoxysilanes; hydrosilylation curatives; and diaminecuratives. In one embodiment, the crosslinking agent is selected fromthe group consisting of sulfur-containing compounds, peroxides, andphenolic compounds.

Crosslinking agents for use in the invention include sulfur-containingcompounds such as elemental sulfur, 4,4′-dithiodimorpholine, thiuram di-and polysulfides, alkylphenol disulfides, and2-morpholino-dithiobenzothiazole; peroxides such as di-tertbutylperoxide, tertbutylcumyl peroxide, dicumyl peroxide,2,5-dimethyl-2,5-di-(tertbutylperoxy) hexane,di-(tertbutylperoxyisopropyl)benzene, tertbutyl peroxybenzoate and1,1-di-(tertbutylperoxy)-3,3,5-trimethylcyclohexane; metal oxides suchas zinc, magnesium, and lead oxides; dinitroso compounds such asp-quinone dioxime and p,p′-dibenzoylquinone-dioxime; phenolic compounds;and phenol-formaldehyde resins containing hydroxymethyl or halomethylfunctional groups. The suitability of any of these crosslinking agentsfor use in the invention will be largely governed by the choice ofelastomers, as is well known to those skilled in the compounding art.

In one embodiment, sulfur containing compounds and the peroxides are thepreferred crosslinking agents, and the sulfur containing compounds aremost preferred. It is understood that mixtures of these crosslinkingagents can be employed, though this is generally not preferred. Theamount of the crosslinking agent can range from about 1 to 10 parts byweight based upon 100 parts of the elastomers in the composition. Sulfurcan be a crystalline elemental sulfur or an amorphous elemental sulfur,and either type can be in pure form or supported on an inert carrier. Anexample of a supported sulfur is Rhenogran S-80 (80% 5 and 20% inertcarrier) from Rhein Chemie.

Crosslinking temperatures and time employed are typical. Temperaturesranging from about 250° F. to about 440° F., and times ranging fromabout 1 minute to about 120 minutes may be employed.

An inventive composition may further comprise one or more thermoplasticpolymers, including, but not limited to, homopolymers and interpolymersof ethylene, propylene, or other olefin-based polymers. Other blendcomponents including other polyolefin materials (for example, EVA, LDPE,POP, POE) can be used to improve melt strength or modify properties.Ethylene-based interpolymers include copolymers or ethylene with butene,propylene, hexene, or octene. An inventive composition may also compriseone or more or more unsaturated diene elastomers (e.g., BR, SBR, NR andIR).

Ethylene-based polymers include copolymers or ethylene with butene,propylene, hexene, or octene. Suitable ethylene-based polymers includehigh density polyethylene (HDPE), low density polyethylene (LDPE),linear low density polyethylene (LLDPE), very low density polyethylene(VLDPE), ultra low density polyethylene (ULDPE), homogeneously branchedlinear ethylene/α-olefin interpolymers and homogeneously branchedsubstantially linear ethylene/α-olefin interpolymers. In one embodiment,the ethylene-based polymer is an ethylene/α-olefin interpolymer. In afurther embodiment, the α-olefin is selected from propylene, 1-butene,1-hexene, or 1-octene.

In one embodiment, the first composition further comprises one or moreother ethylene-based polymers or olefin-based polymers. In anotherembodiment, the first composition further comprises an ethylene-basedpolymer. In a further embodiment, the ethylene-based polymer is selectedfrom an ethylene homopolymer or an ethylene/α-olefin interpolymer. Inyet another embodiment, the first composition further comprises anethylene/α-olefin interpolymer. In a further embodiment, the α-olefin isselected from propylene, 1-butene, 1-hexene, or 1-octene.

As discussed above, the terms “homogeneous” and “homogeneously-branched”are used in reference to ethylene/α-olefin interpolymers, in which theα-olefin comonomer is randomly distributed within a given polymermolecule, and all of the polymer molecules have the same orsubstantially the same ethylene-to-comonomer ratio.

The homogeneously branched ethylene interpolymers that can be used inthe practice of this invention include homogeneously branched linearethylene interpolymers, and homogeneously branched substantially linearethylene interpolymers.

Included amongst the homogeneously branched linear ethyleneinterpolymers are ethylene polymers, which lack long chain branching (ormeasurable amounts of long chain branching, as determined, for example,by 13C NMR), but do have short chain branches, derived from thecomonomer polymerized into the interpolymer, and which are homogeneouslydistributed, both within the same polymer chain, and between differentpolymer chains. That is, homogeneously branched linear ethyleneinterpolymers lack long chain branching, just as is the case for thelinear low density polyethylene polymers or linear high densitypolyethylene polymers, and are made using uniform branching distributionpolymerization processes, as described, for example, by Elston in U.S.Pat. No. 3,645,992. Commercial examples of homogeneously branched linearethylene/α-olefin interpolymers include TAFMER polymers supplied by theMitsui Chemical Company and EXACT polymers supplied by Exxon ChemicalCompany.

The homogeneously branched substantially linear ethylene interpolymersare described in U.S. Pat. Nos. 5,272,236; 5,278,272; 6,054,544;6,335,410, and 6,723,810; the entire contents of each are hereinincorporated by reference.

In addition, the substantially linear ethylene interpolymers arehomogeneously branched ethylene polymers having long chain branching.The long chain branches have the same comonomer distribution as thepolymer backbone, and can have about the same length as the length ofthe polymer backbone. The carbon length of a long chain branch is longerthan the carbon length of a short chain branch formed from theincorporation of one comonomer into the polymer backbone.

Typically, “substantially linear” means that the bulk polymer issubstituted, on average, with 0.01 long chain branches per 1000 carbons(including both backbone and branch carbons) to 3 long chain branchesper 1000 carbons. Some polymers are substituted with 0.01 long chainbranches per 1000 carbons, to 1 long chain branch per 1000 carbons, orfrom 0.05 long chain branches per 1000 carbons to 1 long chain branchper 1000 carbons, or from 0.3 long chain branches per 1000 carbons to 1long chain branch per 1000 carbons.

Commercial examples of substantially linear interpolymers include theENGAGE polymers (available from The Dow Chemical Company), and theAFFINITY polymers (available from The Dow Chemical Company).

The homogeneously branched linear or substantially linear ethyleneinterpolymers are characterized as having a narrow molecular weightdistribution (M_(w)/M_(n)). For the linear and substantially linearethylene polymers, the molecular weight distribution, M_(w)/M_(n), isfor example, less than or equal to 5, preferably less than or equal to4, and more preferably from 1.5 to 4, and even more preferably from 1.5to 3, and most preferably from 2.5 to 3.5. All individual values andsubranges from 1 to 5 are included herein and disclosed herein.

The homogeneously branched substantially linear ethylene interpolymersused in a composition of the invention are known, and they and theirmethod of preparation are described in, for example, U.S. Pat. Nos.5,272,236; 5,278,272 and 5,703,187; which are each incorporated in theirentirety, herein, by reference.

The heterogeneously branched ethylene interpolymers can also be used inthe present invention. Heterogeneously branched ethylene interpolymersinclude interpolymers of ethylene and one or more C₃ to C₈ α-olefins.Homopolymers of ethylene can also be prepared using the same catalyststhat are used to prepare the heterogeneous systems, such asZiegler-Natta catalysts. Both the molecular weight distribution, and theshort chain branching distribution, arising from α-olefincopolymerization, are relatively broad compared to homogeneous linearethylene polymers. Heterogeneously branched ethylene polymers can bemade in a solution, slurry, or gas phase process using a Ziegler-Nattacatalyst, and are well known to those skilled in the art. For example,see U.S. Pat. No. 4,339,507, the entire contents of which isincorporated herein by reference.

Heterogeneously branched ethylene-based interpolymers include, but arenot limited to, linear medium density polyethylene (LMDPE), linear lowdensity polyethylene (LLDPE), very low density polyethylene (VLDPE), andultra low density polyethylene (ULDPE). Commercial polymers includeDOWLEX polymers, ATTANE polymer, TUFLIN polymers, and FLEXOMER polymers(all from The DOW Chemical Company), and ESCORENE LLDPE polymers (fromExxon Mobil).

An ethylene-based polymer may have a combination of two or moreembodiments as described herein.

Suitable propylene-based polymers include propylene homopolymers,propylene interpolymers, as well as reactor copolymers of polypropylene(RCPP), which can contain about 1 to about 20 weight percent ethylene oran α-olefin comonomer of 4 to 20 carbon atoms. The propyleneinterpolymer can be a random or block copolymer, or a propylene-basedterpolymer.

Suitable propylene copolymers include propylene/ethylene,propylene/1-butene, propylene/1-hexene, propylene/4-methyl-1-pentene,propylene/1-octene, propylene/ethylene/1-butene, propylene/ethylene/ENB,propylene/ethylene/1-hexene, propylene/ethylene/1-octene,propylene/styrene, and propylene/ethylene/styrene.

Suitable polypropylenes are formed by means within the skill in the art,for example, using single site catalysts (metallocene or constrainedgeometry) or Ziegler Natta catalysts. The propylene and optionalcomonomers, such as ethylene or alpha-olefin monomers are polymerizedunder conditions within the skill in the art, for instance, as disclosedby Galli, et al., Angew. Macromol. Chem., Vol. 120, 73 (1984), or by E.P. Moore, et al. in Polypropylene Handbook, Hanser Publishers, New York,1996, particularly pages 11-98. Polypropylene polymers include Shell'sKF 6100 homopolymer polypropylene; Solvay's KS 4005 polypropylenecopolymer; Solvay's KS 300 polypropylene terpolymer; and INSPIREpolypropylene resins available from The Dow Chemical Company.

Suitable propylene/α-olefin polymers, containing at least 50 molepercent polymerized propylene, fall within the invention. Suitablepolypropylene base polymers include VERSIFY polymers (The Dow ChemicalCompany) and VISTAMAXX polymers (ExxonMobil Chemical Co.), LICOCENEpolymers (Clariant), EASTOFLEX polymers (Eastman Chemical Co.), REXTACpolymers (Hunstman), and VESTOPLAST polymers (Degussa). Other suitablepolymers include propylene-α-olefins block copolymers and interpolymers,and other propylene based block copolymers and interpolymers known inthe art. Additional propylene-based interpolymers include thosedescribed in U.S. Provisional Application No. 60/988,999 (filed Nov. 19,2007), fully incorporated herein.

Preferred comonomers include, but are not limited to, ethylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-octene, non-conjugated dienes, polyenes,butadienes, isoprenes, pentadienes, hexadienes (for example,1,4-hexadiene), octadienes, styrene, halo-substituted styrene,alkyl-substituted styrene, tetrafluoroethylenes, vinylbenzocyclobutene,naphthenics, cycloalkenes (for example, cyclopentene, cyclohexene,cyclooctene), and mixtures thereof. Typically and preferably, thecomonomer is a C2 or a C4-C20 α-olefin. Preferred comonomers includeethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, andmore preferably include ethylene, 1-butene, 1-hexene and 1-octene.

In another embodiment, the propylene-based polymer is apropylene/α-olefin interpolymer or a propylene/ethylene interpolymer,which each has a molecular weight distribution less than, or equal to,5, and preferably less than, or equal to, 4, and more preferably lessthan, or equal to 3. More preferably the propylene/α-olefin interpolymerhas a molecular weight distribution from 1.1 to 5, and more preferablyfrom 1.1 to 4, and more preferably from 1.1 to 3.

A composition may also contain a functionalized polymer, including, butnot limited to, functional grades of polyethylenes, such as maleic acidesters, acrylic and methacrylic acid esters; acrylonitrile; vinylacetate; and derivatives such as chlorinated and sulfonatedpolyethylenes and copolymers; ionomers; polyvinyl chlorides and theirrelated copolymers, functional and modified grades; polymers of acetaland their related copolymers and modified grades; fluorinated olefinpolymers; polyvinylidene fluoride; polyvinyl fluoride; polyamides andtheir modified grades; polyimides; polyarylates; polycarbonates andtheir related copolymers and modified grades; polyethers;polyethersulfones; polyarylsulphones; polyketones; polyetherimides;poly(4-methyl-1-pentene); polyphenylenes and modified grades;polysulphones; polyurethanes and their related modified grades;polyesters and their related modified grades; polystyrene and theirrelated copolymers and modified grades; polybutylene; polymers ofacrylo-nitrile, polyacrylates, mixtures thereof, and the like.

A composition may comprise a combination of two or more embodiments asdescribed herein.

Process for Forming Articles

Inventive articles can be produced by processes known in the art,including, but not limited to, a coextrusion process, a compressionmolding process, a casting process, or a lamination process. Blendedcompositions can be produced using known methods, such as dry blending,or melt mixing, including compounding via banbury, intermix, dispersionkneader, brabender, Haake mixer, twin screw, single screw extrusion.

An article of the invention may be prepared by selecting the polymercompositions suitable for each layer; forming each layer, and bondingthe layers, or coextruding, compression molding, laminating, or castingone or more layers. Desirably, the article layers are bondedcontinuously over the interfacial area between layers.

In one embodiment, the article is formed by a coextrusion process. In afurther embodiment, the article is formed by coextruding the first layerand the second layer to form a two-layered film.

In one embodiment, the article is formed by a compression moldingprocess. In a further embodiment, the article is formed by compressionmolding a film formed from the first composition and a film formed fromthe second composition to form a two-layered film.

In one embodiment, the article is formed by a casting process.

In one embodiment, the article is formed by a lamination process.

For each layer, typically, it is suitable to melt mix the components ofthe respective compositions and any additional additives. The meltmixing should be carried out in a manner, such that an adequate degreeof dispersion is achieved. The parameters of melt mixing willnecessarily vary depending upon the components. However, typically, thetotal polymer deformation, that is, mixing degree, is important, and iscontrolled by, for example, the rotor-design and the melt temperature.The melt temperature during article forming will depend on the articlecomponents. Typically, after melt mixing, a article is formed bycoextruding, compression molding, laminating, or casting one or morelayers.

In one embodiment, sheets of the article composition can be bonded byheat sealing or by use of an adhesive. Heat sealing can be effectedusing conventional techniques, including, but not limited to, a hot bar,impulse heating, side welding, ultrasonic welding, or other alternativeheating mechanisms as discussed above.

The article compositions of the aforementioned processes may be made toany thickness depending upon the application. In one embodiment, themultilayered articles have a thickness less than, or equal to 3500microns, preferably less than, or equal to, 3000 microns, and morepreferably less than, or equal to 2600 microns. In one embodiment, thearticles have a total thickness of from 50 to 3500 microns, preferablyfrom 100 to 3000 microns, more preferably from 200 to 2600 microns. Thepermeability of the article may also be adjusted depending upon theapplication.

Applications

The invention also provides a variety of parts, comprising at least onecomponent formed from an inventive article. Such parts include, but arenot limited to, belts, hoses, tubes, gaskets, membranes, molded goods,extruded parts, automotive parts, adhesives, inner tubes, engine mounts,tires and tire sidewalls.

Parts can be prepared by injection molding, extrusion, extrusionfollowed by either male or female thermoforming, low pressure molding,compression molding and the like.

The invention provides a tire comprising an inventive article.

The invention provides an inner tube comprising an inventive article. Ina further embodiment, the inner tube is a tire inner tube

The invention provides a hose comprising an inventive article.

The invention provides a belt comprising an inventive article.

The invention provides a tube comprising an inventive article.

The invention provides an automotive part comprising an inventivearticle.

The invention provides an automotive weather strip comprising aninventive article.

The invention provides a vibration damper comprising an inventivearticle.

The invention provides an extruded profile comprising an inventivearticle.

The invention provides a building or construction material comprising aninventive article.

The invention provides a shoe component comprising an inventive article.

The invention provides a wire insulation or a cable insulationcomprising an inventive article.

The invention provides a wire jacket or a cable jacket comprising aninventive article.

As discussed above, the multi-layer articles of the invention can beproduced via coextrusion, compression molding, lamination, casting, andthe like, and can be used for numerous bladder applications includingcushioning articles, equine cushions, bra pads, sportsballs, and thelike.

Additional articles include, but are not limited to, polymer sheets,foams, coatings, computer parts, building materials, householdappliances, electrical supply housings, lawn furniture strips orwebbing, lawn mower, garden hose, refrigerator gaskets, acousticsystems, utility cart parts, desk edging, toys and water craft parts.The structures can be used in roofing applications such as roofingmembranes. The structures can further be used in fabricating componentsof footwear such as a shaft for a boot, particularly an industrial workboot. A skilled artisan can readily augment this list without undueexperimentation.

DEFINITIONS

Any numerical range recited herein, include all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or physical property, such as,for example, amount of a blend component, melting temperature, meltindex, etc., is between 1 and 100, it is intended that all individualvalues, such as, 1, 2, 3, etc., and all subranges, such as, 1 to 20, 55to 70, 197 to 100, etc., are expressly enumerated in this specification.For values which are less than one, one unit is considered to be 0.0001,0.001, 0.01 or 0.1, as appropriate. These are only examples of what isspecifically intended, and all possible combinations of numerical valuesbetween the lowest value and the highest value enumerated, are to beconsidered to be expressly stated in this application. Numerical rangeshave been recited, as discussed herein, in reference to structurethickness, Mooney Viscosity, density, and other properties.

The term “multilayered article,” as used herein, refers to an articlethat comprises a structure with more than one layer or ply.

The term “multilayered film,” as used herein, refers to a structure withmore than one layer or ply.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “polymer,” as used herein, refers to a polymeric compoundprepared by polymerizing monomers, whether of the same or a differenttype. The generic term polymer thus embraces the term homopolymer,employed to refer to polymers prepared from only one type of monomer,and the term interpolymer as defined hereinafter.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, employed to refer topolymers prepared from two different types of monomers, and polymersprepared from more than two different types of monomers.

The term “thermoplastic polymer” or “thermoplastic composition” andsimilar terms, mean a polymer or polymer composition that issubstantially thermally extrudable or deformable, albeit relativelyaggressive conditions may be required.

The terms “blend” or “polymer blend,” as used herein, mean a blend oftwo or more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term, “olefin-based polymer,” as used herein, refers to a polymerthat contains a majority weight percent polymerized olefin monomers (forexample ethylene or propylene), based on the weight of the polymer.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat contains a majority weight percent polymerized ethylene monomers,based on the weight of the polymer.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat contains a majority weight percent polymerized propylene monomers,based on the weight of the polymer.

The terms “comprising”, “including”, “having” and their derivatives arenot intended to exclude the presence of any additional component, stepor procedure, whether or not the same is specifically disclosed. Inorder to avoid any doubt, all compositions claimed through use of theterm “comprising” may include any additional additive, adjuvant, orcompound whether polymeric or otherwise, unless stated to the contrary.In contrast, the term, “consisting essentially of” excludes from thescope of any succeeding recitation any other component, step orprocedure, excepting those that are not essential to operability. Theterm “consisting of” excludes any component, step or procedure notspecifically delineated or listed.

Test Procedures

Mooney Viscosity

The Mooney Viscosity is measured in accordance with ASTM D1646-06 (AlphaTechnologies Rheometer MV 2000) using the test temperature, rotor size,and test times specified for each type of polymer.

For a carbon black coated ethylene/α-olefin interpolymer (preferably anEPDM) interpolymer, the polymer Mooney Viscosity [MV (ML1+4 at 125° C.)]for the interpolymer (no carbon black and no oil) can be determined, byone skilled in the art, by one of two methods as described below. Thefollowing methods are in reference to carbon black coated interpolymers,however, one skilled in the art could use similar methods for othertypes of fillers, or other types of polymer/filer morphologies, such asfiller dispersed within an abraded, or grated, polymer bale. Thefollowing methods could also be modified by one skilled in the art toprovide for the determination of Mooney Viscosity at other temperaturesand/or other test conditions, such as preheat time and/or rotor size.The instrument is an Alpha Technologies Rheometer MV 2000. “PolymerMooney Viscosity” refers to the Mooney Viscosity of the interpolymerwithout any filler (carbon black) and without any oil.

Method 1

For a carbon black coated interpolymer, with no oil or a known amount ofoil, typically less than 2 weight percent oil (known amount, and basedon the weight of the interpolymer) (INT A), and which has a measuredviscosity less than 100 [MV (ML1+4 at 125° C.)] as determined by ASTMD1646-06 (Alpha Technologies Rheometer MV 2000), the polymer Mooneyviscosity of the interpolymer can be determined from a calibration curveas follows. The amount of carbon black in the polymerized interpolymer(INT A) can be determined gravimetrically by selective ashing of thepolymer in a manner to leave the carbon black intact (for example TGA).

An interpolymer (no filler, no oil), corresponding in chemical make-upto the interpolymer of interest, and prepared from the same or similarcatalyst system, and of known polymer Mooney Viscosity [MV (ML1+4 at125° C.)], is melt blended with various levels of carbon black, and therequired amount of oil, to form a range of carbon black filledinterpolymers. Melt blending can be done in a Brabender mixer. Thecarbon black and oil used, is the same as that in the interpolymer ofinterest (INT A). The Mooney viscosity [MV (ML1+4 at 125° C.)] ismeasured for each sample (ASTM D1646-06, Alpha Technologies Rheometer MV2000), and a calibration curve is generated, showing the measured MooneyViscosity as a function of amount of carbon black. A series of suchcalibration curves are generated for several interpolymers (no filler,no oil) of varying viscosities. The data from the generated calibrationcurves are entered into a regression program, such as a MICROSOFT EXCELregression program, and the following information is generated: acoefficient for the carbon black level, a coefficient for the measuredMooney viscosity, and an intercept.

The polymer Mooney Viscosity [MV (ML1+4 at 125° C.)] of the interpolymer(INT A) can be calculated using the data generated from the regressionanalysis, the known level of carbon black in the interpolymer (INTA),and the measured Mooney viscosity [MV (ML1+4 at 125° C.)] of theinterpolymer (INT A).

Method 2

For a carbon black coated interpolymer, with no oil or a known amount ofoil, typically less than 2 weight percent oil (known amount and based onthe weight of the interpolymer) (INT B), and which has a measuredviscosity greater than, or equal to, 100 [MV (ML1+4 at 125° C.)], asdetermined by ASTM D1646-06 (Alpha Technologies Rheometer MV 2000), thepolymer Mooney viscosity can be determined from a calibration curve asfollows. The amount of carbon black in the polymerized INT Binterpolymer can be determined gravimetrically by selective ashing ofthe polymer in a manner to leave the carbon black intact (for example,TGA).

An interpolymer (no filler, no oil), for use in calibration, andcorresponding in chemical make-up to the interpolymer of interest, andprepared from the same or similar catalyst system, and of known polymerMooney Viscosity, is melt blended with a fixed amount of carbon black(for example, from 40 to 60 phr carbon black, based on hundred partsinterpolymer), and a fixed amount of an oil (for example, from 60 to 80phr oil, based on hundred parts interpolymer) to form a first sample.The carbon black and oil is the same type as that in the interpolymer ofinterest (INTB). The amount of carbon black and the amount of oil areeach greater than the respective amounts in the interpolymer of interest(INTB). Additional samples are formed, each having an interpolymer ofdifferent Mooney viscosity, and each having the same amount and type ofboth carbon black and oil as the above interpolymer used forcalibration.

The Mooney viscosity [MV (ML1+4 at 125° C.)] is measured for each sample(ASTM D1646-06 (Alpha Technologies Rheometer MV 2000)). A calibrationcurve is generated, showing the measured Mooney viscosity [MV (ML1+4 at125° C.)] as a function of the polymer Mooney Viscosity [MV (ML1+4 at125° C.)] of the interpolymer.

The carbon-black coated interpolymer (INT B) of interest is nextcompounded with additional carbon black to achieve a final carbon blacklevel, as that used in the samples for calibration, as discussed above.Also the INT B interpolymer is compounded with additional oil to achievethe same oil level, as that used in the samples for calibration asdiscussed above, to form a “modified INT B” interpolymer. The Mooneyviscosity [MV (ML1+4 at 125° C.)] of the modified INT B interpolymer ismeasured. The polymer Mooney Viscosity of the interpolymer can be thencalculated using the calibration curve as described above.

Oxygen Transmission Rate (OTR)

The Oxygen Transmission Rate (OTR) is measured using Oxygen PermeationAnalyzer (Illinois Instruments, Model No. 8000). This instrumentconforms to ASTM F 1307. The cover was removed from both the testchambers by loosening the three knobs, anti-clockwise, and any residualsealant from the bottom half of the chamber was removed. A thin layer ofsealant was added to the rim. A template was used to cut out the samplefilm for analysis. The sample film was placed onto the chamber bottom,and the edges of the film were smoothed, in order to remove any airpockets. The chamber cover was placed back and the three knobs weretightened.

From the main screen, the screen tabs were selected as follows.

“Test Tab” was checked.

“Set Up and Purge Tab” was checked.

“Include Box Tab” both were checked.

“Purge Enabled Tab” was checked.

“Time Test Box” was unchecked.

The sampling rate was selected to ten minutes. The bypass time and purgelevel were set according to Table A below.

TABLE A Bypass Time Purge Level STRUCTURE (mins) (cc/100 in²/day) LowBarrier (OTR values greater than 10 10 30 cc/100 in²/day) High Barrier(OTR values less than 30 1 30 cc/100 in²/day)

After starting the test, the Purge Monitor area indicated the status ofthe bypass and purge routine. The test began when both the pipes andcells were purged (turned green). Oxygen flowed to the top chamber, andnitrogen flowed to the bottom chamber. The test ended by manuallyclicking the “stop button,” when the OTR readings stabilized, and thecorresponding graphed profile reached a plateau.

The densities of the ethylene homopolymers and ethylene-basedinterpolymers, other olefin-based polymers, and other polymers as notedin the standard, are measured in accordance with ASTM D-792-00.

Melt index (I₂) of ethylene homopolymers and ethylene-basedinterpolymers are measured in accordance with ASTM D-1238-04, condition190° C./2.16 kg. The melt flow rate (MFR) of propylene homopolymers andpropylene-based interpolymers are measured in accordance with ASTMD-1238-04, condition 230° C./2.16 kg.

The average molecular weights and molecular weight distributions forethylene-base polymers can be determined with a chromatographic systemconsisting of either a Polymer Laboratories Model PL-210 or a PolymerLaboratories Model PL-220. The column and carousel compartments areoperated at 140° C. for ethylene-based polymers. The columns are threePolymer Laboratories 10-micron Mixed-B columns. The solvent is 1,2,4trichlorobenzene. The samples are prepared at a concentration of 0.1gram of polymer in 50 milliliters of solvent. The solvent used toprepare the samples contains 200 ppm of butylated hydroxytoluene (BHT).Samples are prepared by agitating lightly for two hours at 160° C. Theinjection volume is 100 microliters, and the flow rate is 1.0milliliters/minute. Calibration of the GPC column set is performed withnarrow molecular weight distribution polystyrene standards, purchasedfrom Polymer Laboratories (UK). The polystyrene standard peak molecularweights are converted to polyethylene molecular weights using thefollowing equation (as described in Williams and Ward, J. Polym. Sci.,Polym. Let., 6, 621 (1968)):Mpolyethylene=A×(Mpolystyrene)^(B),where M is the molecular weight, A has a value of 0.4315 and B is equalto 1.0.

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software, Version 3.0. The molecular weights forpropylene-based polymers can be determined using Mark-Houwink ratiosaccording to ASTM D6474.9714-1, where, for polystyrene, a=0.702 and logK=−3.9, and for polypropylene, a=0.725 and log K=−3.721. Forpropylene-based samples, the column and carousel compartments areoperated at 160° C.

Percent crystallinity for ethylene-based and propylene-based polymerscan be determined by differential scanning calorimetry (DSC), using a TAInstruments Model Q1000 Differential Scanning Calorimeter. A sample ofaround five to eight mg is cut from the material to be tested, andplaced directly in the DSC pan for analysis. The sample is first heatedat a rate of about 10° C./min to 180° C. for ethylene-based polymers(230° C. for propylene-based polymers), and held isothermally for threeminutes, at that temperature, to ensure complete melting (the firstheat). Then the sample is cooled at a rate of 10° C. per minute to −60°C. for ethylene-based polymers (−40° C. for propylene-based polymers),and held there isothermally for three minutes. Next, the sample is againheated (the second heat) at a rate of 10° C. per minute, until completemelting. The thermogram from this second heat is referred to as the“second heat curve.” Thermograms are plotted as watts/gram versustemperature.

The percent crystallinity in the ethylene-based polymers may becalculated using heat of fusion data, generated in the second heat curve(the heat of fusion is normally computed automatically by typicalcommercial DSC equipment, by integration of the relevant area under theheat curve). The equation for ethylene-based samples is:

% Cryst.=(H_(f)÷292 J/g)×100; and the equation for propylene-basedsamples is:

% Cryst.=(H_(f)÷165 J/g)×100. The “% Cryst.” represents the percentcrystallinity and “H_(f)” represents the heat of fusion of the polymerin Joules per gram (J/g).

The melting point(s) (T_(m)) of the polymers can be determined from thesecond heat curve obtained from DSC, as described above. Thecrystallization temperature (T_(c)) can be determined from the firstcooling curve.

The structures and processes of this invention, and their use, are morefully described by the following examples. The following examples areprovided for the purpose of illustrating the invention, and are not tobe construed as limiting the scope of the invention.

EXPERIMENTAL Resins

EPDM=NORDEL IP 3640 (Mooney viscosity, ML1+4@ 125° C. (MU)=36-44;

Ethylene, Mass %=53-57; ENB, Mass %=1.4-2.2; Molecular Weight

Distribution=Medium)

Butyl rubber=Lanxess BUTYL 301 (Mooney Viscosity, ML1+8@125° C.(MU)=51+/−5; Unsaturation, mol %=1.85+/−0.20)

These polymer resins typically contain one or more stabilizers.

Representative Procedure—Compression Molded Structures

The individual resins (EPDM and butyl rubber) were each compressionmolded, at 180° C., for two minutes (64 to 74 MPa), in a CarverCompression Molding Machine (MODEL NO. 4394.4PR3400) to form a film.Each film was then cooled at 23° C., for 24 hours. The films (EPDM filmand butyl rubber film) were combined, face to face, and manuallycompressed using a “2 kg roller,” for 30 seconds, to form a single,two-layered film.

A “monolayer” film (Comparative Example 1 and 2) was produced byblending the EPDM and butyl rubber resins in a Haake mixer at 80° C.,for 5 minutes, to form a blended material. The blended material wascompression molded at 180° C., for two minutes (64 to 74 MPa).

Each film (Examples 1 to 4 and Comparative Examples 1 and 2) was placedinto an Oxygen Permeation Analyzer (Illinois Instruments, Model No.8000), and analyzed for oxygen barrier performance, as determined byOxygen Transmission Rate (OTR). Oxygen Transmission Rate was measured at23° C. and 0% relative humidity. The results are shown in Table 1 and 2below.

TABLE 1 OTR Results - Comparison between Monolayer and Two-layered FilmComparative Example 1 Example 1 Film composition 56.4% (EPDM) 56 wt %EPDM/ 43.6% (Butyl*) 44 wt % Butyl* (% based on layer ratio) (wt % basedon total weight of film) Film type Two-layered Monolayer First layer =EPDM Second layer = Butyl* Film Thickness (μm) 390 390 Layer Ratio220/170 N/A (μm EPDM/μm Butyl) OTR (cc/m²/day at 571 ± 1 1566 ± 204ambient atm.) Mean ± SD (n = 2) *Butyl = butyl rubber N/A = NotApplicable

TABLE 2 OTR Results - Comparison between Monolayer Incumbent andTwo-layered Inventive Films to determine the Optimum Level of EPDM/Butylfor Two-layered Film Example Comp. Ex. 2 Example 2 Example 3 Example 4Film composition 25 wt % (EPDM) 25.6% (EPDM) 38.5% (EPDM) 48.7% (EPDM)75 wt % (Butyl*) 74.4% (Butyl*) 61.5% (Butyl*) 51.3% (Butyl*) (wt %based on (% based on film (% based on film (% based on film total weightof thickness ratio) thickness ratio) thickness ratio) film) Film TypeMonolayer Two-layered Two-layered Two-layered Film Thickness 390 390 390390 (μm) Layer Ratio N/A 100/290 150/240 190/200 (μm EPDM/μm Butyl) OTR(cc/m²/day at 465 ± 77 319 ± 4 406 ± 35 414 ± 30 ambient atm.) Mean ± SD(n = 2) *Butyl = butyl rubber N/A = Not Applicable

As shown in Table 1 and Table 2, the Oxygen Transmission Rate (OTR)results demonstrate that the multilayer films, based on a layer of EPDMand a layer of butyl rubber, show a much better (lower) oxygentransmission rate than the monolayer films formed from a blend of theEPDM and butyl rubber.

The results demonstrate that an increased level of EPDM can still beused in conjunction with butyl rubber, provided a two-layered film, suchas one formed by a coextrusion construction, is used to make the finalfilm. The higher level of EPDM in a blend with butyl rubber usuallydecreases barrier properties of the sheet. However, the inventiveexamples have demonstrated that the two-layered films, with a layer ofEPDM and a layer of the butyl rubber, afford increased barrierproperties, which will translate to improved gas retention inapplications, such as an inner tube for tires. The concept of theinvention can also be applied to multilayered films containing more thantwo layers (or plies). Multilayered films can be formed by severalprocesses, including compression molding, coextrusion, lamination, andcast film processes.

Although the invention has been described in certain detail through thepreceding specific embodiments, this detail is for the primary purposeof illustration. Many variations and modifications can be made by oneskilled in the art, without departing from the spirit and scope of theinvention, as described in the following claims.

The invention claimed is:
 1. An article comprising a first layer and asecond layer, and wherein the first layer is formed from a firstcomposition comprising an ethylene/α-olefin/diene interpolymer, anisoprene rubber (synthetic), a natural rubber, a butadiene rubber, astyrene butadiene rubber, a chloroprene rubber, a nitrile rubber, ahydrogenated nitrile rubber, a chlorinated polyethylene, achlorosulfonated polyethylene, an ethylene/propylene rubber, anethylene/diene copolymer, a fluoro rubber, a polyurethane, a siliconerubber, or a combination thereof; and wherein the second layer is formedfrom a second composition comprising a butyl rubber, a halobutyl rubber,polyvinylidene chloride, a brominated polymer derived from a copolymerof isobutylene and p-methyl styrene, a nitrile rubber, a chloroprenerubber, a chlorosulfonated polyethylene, a chlorinated polyethylene, apolyurethane, a fluoro rubber, or a combination thereof, and wherein thearticle does not comprise a fiber reinforcing material.
 2. The articleof claim 1, wherein the first composition is different from the secondcomposition.
 3. The article of claim 1, wherein the second layer isformed with a second composition comprising a butyl rubber, a halobutylrubber, a polyvinylidene chloride, a brominated polymer derived from acopolymer of isobutylene and p-methyl styrene, a nitrile rubber, or acombination thereof.
 4. The article of claim 1, wherein the secondcomposition comprises a butyl rubber, a halobutyl rubber, apolyvinylidene chloride, a nitrile rubber, or a combination thereof. 5.The article of claim 1, wherein the second composition comprises a butylrubber, a polyvinylidene chloride, or a combination thereof.
 6. Thearticle of claim 1, wherein the second composition comprises a butylrubber.
 7. The article of claim 1, wherein the second compositioncomprises a polyvinylidene chloride.
 8. The article of claim 1, whereinthe first composition comprises an ethylene/α-olefin/diene interpolymer,an isoprene rubber (synthetic), a natural rubber, a butadiene rubber, astyrene butadiene rubber, an ethylene/propylene rubber, anethylene/diene copolymer, a silicone rubber, or a combination thereof.9. The article of claim 1, wherein the first composition comprises anethylene/α-olefin/diene interpolymer, a natural rubber, a butadienerubber, a styrene butadiene rubber, or a combination thereof.
 10. Thearticle of claim 1, wherein the first composition comprises anethylene/α-olefin/diene interpolymer, a styrene butadiene rubber, or acombination thereof.
 11. The article of claim 1, wherein the firstcomposition comprises an ethylene/α-olefin/diene interpolymer.
 12. Thearticle of claim 1, wherein the second layer is adjacent to the firstlayer.
 13. The article of claim 1, wherein the article further comprisesa third layer formed from a third composition comprising anethylene/α-olefin/diene interpolymer.
 14. The article of claim 13,wherein the second layer is between the first layer and the third layer.15. The article of claim 1, wherein the article has an OxygenTransmission rate (OTR) less than, or equal to, 600 cc/m²/day at ambientatmosphere.
 16. The article of claim 1, wherein at least onecomposition, independently, further comprises at least one filler. 17.The article of claim 1, wherein at least one composition, independently,further comprises at least one crosslinking agent, one crosslinkingactivator in combination with a fatty acid and one crosslinkingaccelerator.
 18. The article of claim 17, wherein the crosslinking agentis selected from the group consisting of sulfur-containing compounds,peroxides, and phenolic compounds.